1061

Index

Page numbers in italics indicate figures and tables a 2-acetylfuran 834 N,O-Acetal trimethylsilyl ether 217 Acetylpyrroles 834 Acetal substitution 231 Acid anhydrides 414 Acetalization 494, 892 – reaction catalyzed by In(III) 414 – by transition-metal catalysts 892 Acid catalysis 56 – i-Pr3SiOTf-mediated intramolecular – for high chemoselectivity 56 494 Acidity constant 36 – of aldehydes and ketones 444 AcOTf 445 Acetals 473–485, 574–575 Acrolein 15, 55, 764 – Hosomi–Sakurai allylation 475 – 1,3-dipolar cycloaddition 15 – protection 574–575 – Diels-Alder reaction 55 –R3SiX-promoted reactions 473–485 Acrolein derivatives 755 β-Acetamido Ketones 558 Acroleins 192 – One-Pot Multicomponent Synthesis – cycloaddition of 2-substituted 192 558 Acrylamides 194, 517 Acetates 445 – cycloaddition 517 • – conversion of THP and MOM ethers – cycloaddition promoted by BF3 OEt2 445 194 Acetic acid 414 Acrylic acids 193 – reaction catalyzed by In(III) 414 – catalyst 193 acetogenin(−)-mucocin 564 Acrylic esters 295 Acetone cyanohydrin 277 –[2+ 2]cycloaddition reaction 295 Acetonide 481 N-acryliminoacetates 590 Acetophenone 262, 264, 676, 774 – Mannich-type reactions 590 –Bu3SnH reduction 264 3-acryloyl-2-oxazolidinone 614, 667 – catalytic asymmetric cyanation 774 Acryloyloxazolidinone 765 – cyanation, La catalyzed 672 Actinidiolide 953 1,2-trans-acetoxy alcohols 842 Acyclic epoxide 682 4-acetoxy-1,3-dioxane 482 Acyclic epoxy alcohols 785 Acetylene 363, 930–935 – one-pot synthesis 785 – addition of Imines Cu catalyzed Acyclic siloxydiene 998 930–935 N-acyl quinolinium 269 – intramolecular reaction 363 – cyanide additions 269 Acetylenic alcohols 355 N-acyl-α-imino phosphonates 921 Acetylenic Schmidt reaction 1011 O-acyl-cyanohydrins 605 Acetylenic sila–Cope rearrangement 1006 1-acyl-3,5-dimethylpyrazoles 951 – Au catalyzed 1006 2-acyl aziridines 612

Acid Catalysis in Modern Organic Synthesis.EditedbyH.YamamotoandK.Ishihara Copyright  2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 978-3-527-31724-0 1062 Index

N-acyl thiazolidine-2-thiones 741 Adjacent Basic Sites 60 Acyl-1,3-oxazolidin-2-ones 614 Aflatoxin B2 6 Acyl-Claisen rearrangements 147 Ag(I) complexes 964 Acyl-Pictet–Spengler reaction 73 Ag(I) Lewis acids 987–1011 Acylal 445 Agelastatin A 443 – formation and hydrolysis 445 AgNO3 991 Acylals 575 AgNTf2 989, 991 – formation and Cleavage 575 AgOAc–PHOX complex 1000 6β-acylamido-5α-steroids 570 AgOAc–QUINAP complex 1000 Acylation 408, 409, 566–567, 574 AgOTf 990, 994 – by Bismuth salts 566 Al catalysts for ene reactions 256–260 – In(III) Lewis acids catalyzed 408 – Al catalyzed 256–260 – of alcohols and phenols 574 – substrates 256 – of electron-rich aromatic compounds Al(III) Lewis acids 241–336 409 – preparation 248, 251 Acylation reaction 245–247 Al(Oi-Pr)3 274, 276, 331 – Al(III) catalyzed 245–247 Al(salen) complex 272, 284, 291 Acylhydrazone 197 – structure 291 – reaction with cyclopentadiene 197 Al[(R,R)-salen]Cl complex 293 Acylhydrazones 11 Al[(S,S)-salen]Cl 291 – enantioselective allylation 11 Al[(S,S)-salen]N3 291 N-acylhydrazones 471, 911 Alanine methyl ester imine 975 – enantioselective free-radical additions – alkylation 975 911 AlAr3(THF) 732 N-acylhydrazones 399 ALB-cyclohexenone complex 287 – In(OTf)3 activated 399 Alcohols 40, 414, 416, 446, 499–502, Acylhydrazono ester 160 573–574, 581, 990, 1009 N-acylimidazoles 690 – acetylation with acetic anhydride acylimidazolesN-acylimidazoles 40 – epoxidation 690 – acylation 574 N-Acyliminium generation 399 – catalytic halogenation 581 N-acyliminium ion 398, 496 – chlorination catalyzed by InCl3 3-acyloxazolidin-2-ones 614 416 N-acyloxazolidinone 754, 1050 – intramolecular addition 990 N-acyloxazoline 142 – intramolecular additions Au catalyzed Acyloxy borane catalyst 211 1009 – chiral 211 – methoxymethylation 573 Acyloxyborane 211 –R3SiX-promoted reactions 499–502 Acyloxyborane catalyst 188, 189, 190, 216 – reaction catalyzed by In(III) 414 N-acylpyridinium ions 495 – silylation 446 Acylpyroles 83 Alcoholysis 571 N-acylpyrroles 690, 709 – of epoxides 571 – addition reaction 709 Aldehyde 553–554, 728, 736, 767 – epoxidation 690 – addition of triethylaluminum 728 Acylzirconocene chlorides 497 – allylation with BINOL-Ti complex Adamantane 370 736 – carbonylation 370 – allylation with Ti-complex 736 Adamantanone 546 – asymmetric allylation Ag catalyzed Addition reaction 144–147, 162–169, 1003 396–400 – cycloaddition 767 –C=N 396–400 – remote stereocontrol of allylation – Zn(II) catalyzed 162–169 553–554 1,4-Addition reaction 391–396 Aldehyde acetals 483 Adjacent amine group 61 Aldehyde tris(trimethylsilyl)silyl 487 Index 1063

Aldehydes 11, 256, 267, 268, 271, 299, 302, –InCl3 catalyzed tandem reaction 356, 381–391, 435, 442, 443, 444, 451, 453, between arylamines and γ 435 455, 458, 485, 508, 536, 552–553, 591, 603, –InCl3-catalyzed deoxygenation of 642, 649, 649, 650, 651, 722–725, 728, aromatic 442 731–733, 736, 745, 760, 878, 880, 992, 993, –Me3Al promotes [2 + 2]cycloaddition 1005 299 – 1,2-additions 381–391 – mukaiyama aldol reaction 485 – acetalization 444 – passerini-type reaction 508 – addition of allylsilane 732, 736 – protection 444 – Al catalyzed cycloaddions 302 –(R2AlCl)-induced intermolecular ene – alkynylation 1005 reaction 256 – alkynylation catalyzed by – reaction of diketone 745 lnCl3 –TMSCl 384 – reaction with diethyl – alkynylation In(OAc)3 –RuCl3catalyzed cyanophosphonate 267 390 – reagent for asymmetric alkylation – allylation Cr catalyzed 880 728 – allylation Yb(OTf)3 catalyzed 647 – reagents for the enantioselective – arylation 732 addition 725 – asymmetric addition 878 –reationGaCl3 Catalyfed 356 – asymmetric addition of alkyl groups – Sc(OTf)3-catalyzed allylation 591 724 –SnCl2 mediated allylation 536 – asymmetric alkylation, Ti-complex – strecker-type reaction of 650 mediated 722 Aldimine 80 – asymmetric alkynylation 458 – by quanidium salt catalyst 80 – asymmetric allylations 455 Aldimine–Yb(OTf) complex 641 – asymmetric diethylzinc addition 723 3 Aldimines 73, 75, 181–182, 591, 642, 651 – asymmetric vinylation 731 – competition reaction 651 – bromoallylation 552–553 – competition reaction of 642 – catalytic allyltitanation 733 – from tryptamine 73 – catalytic enantioselective allylboration – hydrocyanation 75 11 – hydrophosphonylation Al-mediated – chemoselective oxathioactalization 272 603 – competition reaction 651 – Sc(OTf)3-catalyzed allylation 591 – competition reaction 642 – Zn(II) catalyzed 181–182 – competitive allylation reaction 649 Aldol products 85 – cyanation 649, 768 Aldol reaction 118–119, 142–144, 154–160, – cyanoalkoxycarbonylation methyl 211, 213, 250–256, 377–381, 447, 506, cyanoformate 268 537–545, 589, 606–607, 636, 637, 739–747, – cyanosilylation with TMSCN 268 825–834, 994, 996, 1001, 1002 – cyclotrimerization of catalyzed by – Al catalyzed 250–256 – asymmetric N-nitroso 1001 InCl3 453 – dithioacetalization 443 – B(III) Lewis acid promoted 209 – enantioselective addition Ag catalyzed –BINAP•silver(I)-catalyzed asymmetric 992 994 – enantioselective alkylation with – by In(III) Lewis acids 377 Grignard reagents 264 – by scandium triflate 589 – enantioselective allylation 993 – catalyzed by lanthanide triflate 637 – enantioselective – chiral catalysts for catalytic hydrophosphonylation reactions 271 enantioselective 211 – HDA reaction 760 – Cu catalyzed 911–919 – hydrophosphonylation Al-mediated – diastereo- and enantioselective 996 272 – direct asymmetric,of diazoester – In(OTf)3-catalyzed reaction 451 Zr-Binol catalyzed 834 1064 Index

Aldol reaction (contd.) – intermolecular hydroamination 1010 – enoxytrichlorosilanes using chiral – intramolecular alkoxymetalation 990 Lewis base catalysts 506 – nickel-catalyzed carbonyl-ene type –In(OAc)3-enhanced Ru-catalyzed reactions 256 447 3-(2-alkenoyl)-2-oxazolidinones 875 – lanthanide Lewis acid catalyzed 636 N-(α,β-alkenoyl)oxazolidinones 141 –ofchiralsyn and Alkenyl enolates 826 anti-α-methyl-β-protected-oxy – diastereospecific synthesis 826 aldehydes 213 Alkenyl trichloroacetate 994 – scandium and yttrium catalyzed Alkenylnitrone 847 606–607 Alkenylzirconocene 826 – Sn(II) and Sn(IV) Lewis acid based Alkolysis 282 537–545 – Al(OTf)3-catalyzed 282 – Ti catalyzed 739–747 Alkoxo titanium complexes 796 – 2-trimethylsilyloxyfuran with 2-Alkoxy-2-phenylethanol 1049 aldehydes 745 1-alkoxy-3-nitroalkanes 479 – with Lewis acids 142–144 2-alkoxy-1,4-pentadien-3-one 616 – with LPDE 118 β-alkoxy carbonyl compounds 473 – with trimethoxysilyl enolates 1002 Alkoxy dienones 617 – zirconium catalyzed 825–834 Alkoxyazetidines 990 – Zn(II) catalyzed 154–160 N-alkoxycarbonylamino sulfones 555 Aldol-tishchenko reaction 702–706, 706, Alkoxyepoxides 280 707, 834 Alkoxysilanes 470 – lanthanide catalyzed 702–706 Tert-alkyl chloride 242, 244 – reaction pathway 706 Tert-alkyl fluoride 242 – using a La(OTf)3/(R)-BINOL/BuLi Tert-alkyl–alkynyl coupling 242, 244 catalyst 707 2-alkyl-2-adamantanol 181 – with chiral Yb(OTf)3 complex 707 2-alkyl-2-aryl-3,4-dimethyl-5- – Zr catalyzed 834 phenyloxazolidines 617 Aldol-type additions 917, 919 4-alkyl-1,3-dioxanes 482 – of malonic acid hemithioesters to Alkyl alkynes 796 aldehydes 917 – intermolecular hydroamination 796 – of nitriles to ketones 919 Alkyl aluminum 301 Aldol-type reaction 209–214, 473–474, 495 Alkylarylsulfoxides 786 – acetals and subsequent elimination of – asymmetric synthesis 786 tetrahydrothiophene 495 Alkyl dimethylsilyl ethers 485 – boron Lewis acids promoted 209 Alkyl halides 449 – with silyl enolates 473–474 – coupling reactions 449 Aldoxime 847 Alkyl hydrazones 680 – cascade reaction Hf catalyzed 847 Alkyl lithiums 126 Aliphatic alkynes 941 Alkyl siloxanes 470 – addition, reactions, Cu catalyzed 941 Alkyl silyl ethers 604 Aliphatic amines 605 Alkyl transfer reaction 243 – carbomethoxylation 605 Alkyl-Selective Addition to Ketones 179–181 Alkali Metal Salts 109–112 Alkylaluminum chloride 256 – Lewis acidity 109–112 Alkylamines 794 Alkene cyclopropanation 882 – intermolecular hydroamination 794 – Ru(II) porphyrin-catalyzed 882 1,1-alkylaryl-alkenes 609 Alkene-siloxyalkyne carbocyclizations 47 α-tert-alkylated ester 242, 243 Alkenes 256, 407, 578–579, 988, 990, 1010 Alkylation 144, 229, 241–244, 263, 409, 722, – addition of thiolacetic acid and thiols 837, 973–976 407 – Al(III) catalyzed 241–244 – hydroalkylations 988 – B(III) Lewis acid catalyzed 229 – hydroarylation 578–579 – by titanium complexes [13] 722 Index 1065

– catalyzed by Zr or Hf chloride 837 – of aldehydes catalyzed by – Cu catalyzed 973–976 InCl3 –TMSCl 384 – Lewis Acid Activated 367 – of ketones 162 – of alanine methyl ester imine 976 – tert-Alkyl chloride and bromide 244 – of aldehydes 144 Alkynylation asymmetric 458 – of aldehydes with Grignard reagents – In(III)–BINOL catalyzed 458 263 o-alkynylbenzaldehyde 1008 – of arenes 409 Alkynyldichlorogallium 365 – of heteroatom nucleophiles 244 Alkynylgallium 372 – of pentamethylbenzene 1004 Alkynyltrimethylsilanes 414 Alkylation reaction 247–248, 565 Allenamides 969 – Al catalyzed 247–248 Allene 222 – by bismuth salts 565 1,2-allenic ketones 592 Alkyldichloroboron Lewis acid catalyst 190 Allenoate-Claisen rearrangement 174 O-alkylhydroxylamines 612, 708 Allenyl enolate 826 – 1,4-addition 708 – Zi rconocene-derived 826 – conjugate addition 612 Allenyl-tributylstannane 506 Alkylidene malonates 942 Allenylation 478 Alkylidenecyclopropanone silyl acetal 523 – intramolecular using propargylsilanes – regioselective ring-opening 523 478 Alkylithium 359 Allenynes 1008 – cycloisomerization 1008 (alkylsulfinyl)methylphosphonates 787 Allo-phenylnorstatine 700 Alkyne 439, 794 Allonate/Claisen tandem reaction 533 – hydroamination 794 Allyl 2,4-dimethylphenyl ethers 329 – intramolecular allylstannylation 439 – Claisen rearrangement 329 Alkyne π acid 363 Allyl alcohol 850 Alkyne-propargylic acetates 1009 – ZACA reaction 850 – cyclization 1009 Allyl aminoacetates 331 Alkyne–carbonyl coupling reactions 988 Allyl ester 856 – inter- and intramolecular 988 Allyl halides 536 Alkynes 361–368, 403, 405, 794, 1005, 1011 –SnCl2 mediated allylation 536 – addition reaction catalyzed by Allyl morpholine 148 In(OTf)3 405 Allylphenylethers 327 – addition reactions 403–407 – aromatic Claisen rearrangement 327 – carbometalation 365–368 Allyl vinyl ethers 327 π – complexation 361–365 – tandem Claisen – gold(I)-catalyzed intramolecular rearrangement/alkynylation reaction addition reaction 1005 327 – intermolecular hydroamination 794 Allyl(enoxy)silane 503 – intramolecular carbothiolation 1011 Allyl–In(III) complex 455 1-alkynes 365 Allylation 9, 10, 15, 16, 119, 168, 261, 383, Alkynyl aluminum 282 388, 389, 414, 415, 430, 440, 455, 471, 476, 2-alkynylanilines 440 504, 534–536, 646, 647, 649, 645–649, – intramolecular cyclization 440 732–739, 840, 880, 890, 992, 1002 O-alkynylarylaldimines 440 – aldehydes in the presence of benzoic Alkynylation 162, 168, 244, 261, 384, 390, acid 646 415 – aldehydes with allylsilane catalyzed by – enantioselective 162, 168 Yb Lewis acid 647 – 2-fluorobenzaldehyde 261 – aldehydes with allylstannane catalyzed – of acid chlorides catalyzed by InBr3 by Yb(OTf)3 646 415 – allenylstannane catalyzed by Yb(OTf)3 – of aldehydes 390 649 – of aldehydes Au catalyzed 1005 – and prins cyclization 430 1066 Index

Allylation (contd.) Allylations 838–840, 935–937 – asymmetric 455, 992 – of ketones, Cu catalyzed 935 – benzaldehyde 736 – with Allylstannanes Zr-catalyzed – by of titanium Lewis acids 732 838–840 – by Ti-BINOL-Boroxine combined Allylboration 260 system 16 – Al mediated 260 – catalyzed by In(OTf)3 440 Allylboration of aldehydes 217 – diastereoselective 534 Allylboron reagent 218 – dihydrofurans 387 Allylboronate 609, 937 – dihydropyrans 387 – transmetallation 937 – enantioselective 10 Allylchlorosilane 431 – intramolecular of oxocarbenium ions Allyldiisopropoxyborane 8 with allylsilanes 476 Allyldimethyl(2-pyridyl)silane 994 – lanthanide Lewis acid catalysis Allyldimethylsilyl chloride 442 645–649 Allylgallium 355, 357, 365, 371 – nucleophilic 534 Allylic 414 –ofN-acylhydrazones derived from Allylic alcohol 179, 768, 782 aldehydes and ketones 504 – cyclopropanation 768 – of acid chlorides 414 – enantioselective epoxidation 782 – of acid chlorides catalyzed by InBr3 Allylic alkylation 870 415 – asymmetric by POZ 870 – of aldehyde or ketone-derived Allylic bromide 386, 439 acrylhydrazones 9 – intramolecular reaction 439 – of aldehydes 15, 388 Allylic epoxy alcohols 785 – of aldehydes Ag catalyzed 993 – one-pot synthesis 785 – of aldehydes with allyl tin 880 Allylic halogenation 502 – of aldehydes with allylic –R3SiX-promoted 502–503 trimethoxysilanes 1002 Allylic indium 414 – of aldehydes with allyltributyltin Allylic Rearrangement 569 catalyzed 645 – glycols 569 – of aromatic aldehydes 261 Allylic silanes 14, 200 – of benzaldehyde with allyltributyltin – annulation 200 840 Allylic Substitutions 115–117 – of carbonyls 471 – LPDE mediated 115 – of epoxides 648 Allylic trimethoxysilanes 997 – of gem-diacetates 389 Allylmagnesium bromides 354 – of hydrazones 168 Allylmagnesium halide 372 – of imines catalyzed by lanthanide N-allylmorpholine 147 triflate 649 Allyloxysilanes 835 – of imines with allystannanes 733 π-allylpalladium 494 – of ketones 385 π-allylpalladium chloride dimer catalyst – of the aldehydes with tributylallyltin 890 736 Allylphenol 851 – Pd(II) and Pt(II)-catalyzed 890 – ZACA reaction 851 – promoted by InCl3 383 2-allylphenol 429 – trifluoroacetaldehyde 387 Allylsilane 217, 471, 476, 503, 848, 937 – using allylsilanes 388 –[2+3] cycloaddition 848 – with Lewis acids 119 – transmetallation 937 Allylation reactions 552–554, 591–592, E-allylsilanes 792 609–611 Allylsilicates 472 – Bismuth(III) Lewis Acids promoted Allylsiloxane 216 552–554 Allylstannanes 382, 385, 534, 647, 732, 838, – Sc(OTf)3 catalysis 609 890 – Sc(OTf)3-catalyzed 591 Allyltin reagents 387 Index 1067

Allyltitanium 732 – intramolecular additions Au catalyzed – preparation 732 1009 Allyltributyl stannane 455 – reaction catalyzed by In(III) 414 Allyltributyltin 335 – strecker-type reaction 650 Allyltrichlorosilane 504, 506 α-aminonitrile 66, 558, 832 Allyltriisopropylsilane 200 – synthesis 558 Allyltrimethoxysilane 168, 992, 993, 994 (1R,2S)-2-amino-1,3-diphenyl-1-propanol Allyltrimethylsilane 261, 389, 475 1048 Allysilane 647, 733 1-Amino-3,4-diols 89 Aluminate complexes 283 α-amino iminolactones 351 Aluminum 266 β-amino esters 608 – pentavalent 266 β-amino ketones 608 Aluminum alkoxide 277, 284 β-amino-α-hydroxycarboxylic acids 400 – preparation 284 1-amino-2-indanol 895 Aluminum dialkoxide 266 Amino alcohol 628, 853 Aluminum dodecatungstophosphate 244, – selective O-acylation 628 245, 283 syn-β-amino alcohol 156 Aluminum dodecylsulfate trihydrate 287 Amino alcohol zinc complex 1051 – preparation 287 1,3-amino alcohols 380 Aluminum phenoxide 304 – catalyzed by InCl3 synthesis 380 aluminum phenoxides sterically hindered Amino Group 575–576 262 – protection 575 – structures 262 α-Amino Phosphonates 400, 498, 558, 921 Aluminum triisoperoxide 804 – synthesis 558 Aluminum tris(2,6-diphenylphenoxide) 252, Aminoacetals 496–498 522 –R3SiX-promoted reactions 496–498 Aluminum Trans-1,2-aminoalcohol derivatives 279 tris(2-α-naphthyl-6-phenylphenoxide) 328 Aminoalkenes 46, 628, 799 Aluminum – asymmetric hydroamination 628 tris[2,6-bis(4-fluorophenyl)phenoxide] 287 – cyclization 46, 799 Amidation 991 N-(α-aminoalkyl)benzotriazoles 638 – intramolecular 991 Aminoalkynes 799 Amidinium Salts 82 – intramolecular hydroamination 799 Amidoalkylation 217, 536 Aminoallenes 799, 800 – diastereoselective intramolecular – asymmetric intramolecular 217, 536 hydroamination 800 2-amidofurans 313 para-aminoarylketones 567 – Diels–Alder/rearrangement reaction 2-aminochalcones 396 313 – cyclizations catalyzed by InCl3 –SiO2 Amidolysis 612 396 Amination 973–976, 1001 α-Aminohyrazones 89 – Cu catalyzed 973–976 3-aminoimidazoles 600 – of silyl enolates with azo diester Aminolysis 282, 572 compounds 1001 – Al(OTf)3-catalyzed 282 Amine 590 – aziridines 572 – immobilizations 590 Aminolysis reactions 569 Amine base–chiral Lewis acid 141 2-Aminotetrahydropyrans 496 Amine Catalysts 80–83 Ammonium Salts 83 – protonated 80–83 Anhydrides 233 Amines 396, 414, 446, 453, 650, 1009 – ring opening 233 – N-tert-butoxycarbonylation 446 Anilines 350, 368 – condensation 453 –BCl3-promoted o-acylation of 350 – conjugate addition of 396 – direct o-ethynylation 368 1068 Index

Anilinium salt 50 N-arylaldimines 423, 424 –acidity 50 – imino Diels–Alder reaction 423 p-Anisaldehyde 25 –InCl3 catalyzed reaction 424 o-anisaldehyde 928 Arylalkynes 1008 Anisole 835 – Intramolecular [4+2] cycloadditions – acylation 835 1008 Annulation reaction 616, 627 Arylbis(triflyl)methanes 41 – by scandium and yttrium 616 –synthesis 41 – Y complex 627 Arylboron dichloride 1025 Anti-β-azido-α-hydroxyamides 691 Arylboronic acid 221 Anti-aldol reactions 142 4-arylbutyric acids 566 –byMgCl2 142 2-Arylcycloalkanones 1004 Anti-aldol-type adducts 139 Aryldibromoborane 1027 Anti-Markovnikov aldimine product 796 Aryldimethoxyboranes 1027 l-anti-sphingosine 829 Arylglyoxals 436 (R)-arbutamine 700 – three-component reaction 436 Arbuzov rearrangement 500 N-Arylidene glycine methyl ester 153 Arene 363, 369, 1004 2-(arylidene)malononitrile 801 – benzylation 1004 Arylidene malonate 907 – intramolecular reaction 363 2-arylindoles 438 – Lewis Acid Activated 369 Aryliodine bis(trifluoroacetate)s 502 Arene-siloxyalkyne carbocyclizations 46 Arylisonitriles 351 Arene–platinum complex 350 1-arylnaphthalenes 351 Arene–siloxyalkyne carbocyclization 989 arylnaphthalenes1-arylnaphthalenes 355 Arenes to alkynes 405 Arylnitroso dienophiles 596 – Friedel–Crafts type addition 405 Aryloxo titanium complexes 796 Arenynes 1008 2-arylthio-acetophenones 202 – cyclization Au catalyzed 1008 – cyclization 202 Aromatic alkylation 369 2-arylthio-ketones 202 Aromatic Claisen rearrangement 329 aryltins 578 – MABR-mediated 329 Aryltitanate reagents 491 Aromatic substitution 410, 408–413, 655 Aryltitanium 731 – achiral lanthanide Lewis acid catalysis 1-aryltriazenes 226 655 – cross-coupling 226 – of indoles catalyzed by In(III) salts Aryltrifluoromethyl ketones 144 410 Arylzinc reagents 491 N-Aroyltrifluoromethane sulfonamides Asymmetric catalysis 454–458, 624 –pKa Value 37 – by chiral indium complexes 454–458 N-aroyltrifluoromethane sulfonamides 37 Asymmetric Diels–Alder reaction 113, 456, – Hammett σp 37 614 2-aryl-2,3-epoxy acylate 205 – catalyzed by chiral In(III)–BINOL – acyclic 205 complex 456 – cyclic 205 – mediated by alkali metal Lewis acid 1-aryl-1-alkylhydrazines 798 113 Aryl amines 437 – of cyclopentadiene with Aryl cyclopropyl ketones 487 3-acryloyloxazolidin-2-one 614 Aryl halides 178 Asymmetric Epoxidation 687–691 – exchange reactions 178 – lanthanide catalyzed 687–691 Aryl iodide 987 Asymmetric hetero-Diels–Alder reaction Aryl methyl sulfoxides 786 614 Aryl nitroolefins 761 – of benzaldehyde with the Aryl pinacol 58 Danishefsky’s diene 614 Arylsilylenolethers 607 Asymmetric ionic Diels–Alder reaction 562 N-aryl tetrahydroisoquinolines 935 – for the synthesis of cis-decalins 562 Index 1069

Asymmetric reduction 454 1-azafenestranes 324 – In(OTf)3-catalyzed 454 1-azaspirocyclic product 204 Asymmetric ring-opening 777 Azetinyl thiazolidine-2-thiones 741 – cyclohexene oxide 777 Azidation 416 – of meso epoxides 777 β-Azido hydrins 1049 ‘Ate-complexes’ 721 Azido trienone 313 ATNP 329 – Diels–Alder/Schmit–Aubereactionof´ Atom transfer 234 313 Atom transfer cyclization 439 Azidolysis 527 Atom transfer radical polymerization 1020 – regio- and stereoselective 527 ATPH 264, 308, 324, 332 Aziridination 228, 896 – application 264 – catalytic asymmetric 228 Au(I) Lewis acids 987–1011 – of aryl imines with diazoacetate, Fe Au(III) Lewis acids 987–1011 catalyzed 896 AuCl3 1010 Aziridination reactions 882 AuCl3/AgOTf 1004, 1005 – of aryl imines 882 Aza Diels–Alder reaction 91, 92, 96, 663, Aziridine 227 652, 652, 656–663, 664, 845, 953, 956 – cis trans 227 – catalytic asymmetric 656–663, 663 (Z)-aziridine 602 – catalyzed 663 Aziridine ring opening 443 – Cu catalyzed 953 – catalyzed by In(OTf)3 443 – cyclohexenone with aldimines 96 Aziridine-2-carboxylate 495 – enantioselective 956 Aziridines 93, 400–403, 404, 528, 572, 594, – of Brassard diene 92 683, 880 –ofDanishefsky’sdiene 91 – aminolysis 572 –ofN-tosyl α-imino ester with – reaction catalyzed by InCl3 404 Danishefskys diene 953 – reaction with acid anhydride 594 – lanthanide triflate catalyzed 652 – ring opening 400–403 – postulated transition state model for – ring opening with TMSCN 683 664 – ring-opening reaction 528 – three-component 652 – synthesis by phosphoric acid catalysts – Zr catalysts 845 93 Aza Henry reaction 71, 76, 82, 926–930 – thiolysis 572 – β-amino nitro compounds 76 2,3-aziridino alcohols 528 – ammonium salt 82 – stereoselective rearrangement 528 – Cu catalyzed 926–930 Aziridinyl alcohol 153 Aza Michael addition 52 Aziridinyl alcohol ligand 152 Aza(bisoxazolines) 978 Azlactone 78 –CuCl2/polymer-bound 978 – kinetic resolution 78 Aza-Claisen rearrangement 327 Azomethine imines 966 – of zwitterionic allyl–vinylammonium – kinetic resolution 966 complexes 327 – with electron-deficient alkynes 966 Aza-Diels–Alder reactions 595 Azomethine ylide 151, 152, 964, 965, 999 Aza-Michael reactions 18, 19, 662 – cycloaddition 964 –ofN-acylpyrroles catalyzed by YLB – 1,3-dipolar cycloaddition 999 19 – enantioselective cycloaddition 965 – of alkoxylamines and catalytic 2-azopyridine 998 asymmetric fluorination of β-Keto esters 662 b – of methoxyamine catalyzed by B(III)Lewis acids 187 (S,S,S)-YLi3tris(binaphthoxide) 18 B(C6F5)3 55 Azadienes 424 Baeyer–Villiger oxidation 545–546 – imino Diels–Alder reaction 424 – Sn(II) and Sn(IV) Lewis acid 2-azadienes 956 promoted 545 1070 Index

Baeyer–Villiger Reactions 148–149 Benzoyl cyanide 774 Balanol 893 Benzoylation 978 BAMOL 26 – Cu(II)-catalyzed 978 Barbier-type allylation 648 Benzoylhydrazones 505 – catalyzed by La(OTf)3 648 N-benzyl imines 210 –ofα,α-difluoropropargyl bromide N-benzyl imino–aldol adducts 210 catalyzed by Eu(OTf)3 648 (R,R)-3-aza-3-benzyl-1,5-dihydroxy-1,5- Barbier-type reaction 647 diphenylpentane 762 Bayer reaction 249 2-benzyl-4-chloro-tetrahydropyran 571 – of indole 249 4-(S)-benzyl-((E)-2-butenoyl)-1,3-oxazolidin- Baylis–Hillman acetates 419 2-one 615 Baylis–hillman adducts 221 Benzyl diphenylphosphinates 499 – β-bromo 221 Benzyl meldrum’s acids 599 Baylis–Hillman reaction 67, 149, 781–782 Benzyl sulfide 855 – Ti catalyzed 781–782 N-benzylanilines 368 Beckmann Rearrangement 568 – o-ethynylation with chloroacetylene Benzaldehyde 15, 58, 221, 355, 723, 736, 368 759 Benzylation 484 – allylation with BINOL-Ti complex – of alcohols with benzaldehydes and 736 Et3SiH 484 – asymmetric allylation 15 – of arenes 1004 σ-benzaldehyde iron complex 895 N-benzylhydroxylamine addition 145 – catalystic asymmetric diethylzinc O-benzylhydroxylamine 612, 942 addition 723 – asymmetric conjugate addition 612 –phenylation 58 Benzylic alcohol 414, 553 – reaction with but-3-yn-2-one 221 – deoxygenative allylation 553 Benzannulation 1008 – reaction catalyzed by In(III) 414 – gold-catalyzed 1008 Benzylic alcohols secondary 442 Benzene 247 N-benzylidene-2-hydroxyaniline 663 – Al catalyzed alkylation 247 (S)-S-N-benzylidene-p-toluenesulfinamide (S)-3-(benzene-fused-phthalimido)-2- 545 piperidinonate 868 Benzylidene acetal 792 Benzimidazole 436, 563 – deuteride addition 792 – 2-substituted 436 Benzylidene-β-diketones 1006 – synthesis 563 Benzylideneaniline 762 1,5-benzodiazepines 436 N-benzylideneaniline 880, 882, 883, 998 – synthesis of catalyzed by InBr3 436 N-benzylidenebenzylamine N-oxide 664 Benzofuran 232, 436 Benzyloxyacetyl chloride 147, 148 –InCl3 catalyzed three-component α-benzyloxyaldehyde 758 reaction 436 N-benzyloxycarbonyl-2-methoxypiperidine Benzoic acids 37 620 – Hammett σp 37 – nucleophilic substitution 620 –pKa Value 37 Benzyloxysilanes 835 • Benzophenone imine glycine methyl ester BF3 Et2O 380, 539 • 922 BF3 OEt2 194, 196, 204, 207, 208, 213, 224 2-benzopyrylium-4-olate 614 – by nucleophilic substitution 224 2-benzopyryrium-4-olate 667 – selectivity 207 • p-benzoquinone monoimine 200 BF3 OEt2 zinc(II) iodide catalyst 220 • Benzoquinoneimine 232 BF3 OEt2 catalysis 200 1,4-Benzoquinones 7, 766 Bi(II) Lewis acids 551 + – asymmetric [3 2] cycloaddition 7 Bi(N(SO2C10F21)2)3 catalyst 574 – cycloaddition 766 Bi(NTf2)3 566 Benzothiophenes 202 Bi(OTf)3 572 • – 3-aryl-substituted 202 OBi(OTf)3 xH2O 556 Index 1071

• Bi(OTf)3 xH2O 565, 577 BINOL derivative 318, 336 • Bi(OTf)3 xH2O catalysis 574 –3,3-disubstituted 318 • Bi(OTf)3 xH2O–chiral bipyridine complexes –3,3-silylated 336 556 BINOL ligands 164, 751 1,1 -Biaryl-2,2 -dimethanol 86 – bifunctional 164 1,1 -Biaryl-2,2 -diol 318 – bridged multitopic 751 Bicyclic endo-chromium complex 317 BINOL zirconium catalyst 840 Bicyclic amine 601 – asymmetric activation of chiral 840 bicyclo[2.2.2]diazaoctanes 327 BINOL-derived ligands 615 Bicyclo[m.n.l]Alkanones 563 BINOL–Ca(II) catalyst 150 Bicycloketone synthesis 27 BINOL–Ti 742 Bicyclopentanones 803 BINOL–Ti catalyst 748, 777–779, 790 Bifurans 438 BINOL–Ti complexe 734, 735, 768, 777, 787 Biginelli reaction 432 – asymmetric catalysis 735 Biginelli condensation 600 – preparation 734 – by Sc(OTf)3 600 BINOL–Ti oxide 741 Biginelli reaction 97, 434, 557–558, 669, 670 i BINOL–Ti(O Pr)2 750 – Bi(III) Lewis Acids 557–558 i BINOL–Ti(O Pr)2 complex 735 – catalyzed by InCl3 434 BINOL–TiCl2 741 – promoted by chiral Yb catalyst 669 BINOL–TiCl2 complex 757 – transition state model 670 BINOL–TiF2 736 Bimetallic lanthanide catalyst 682 BINOL–titanium complex 751 Bimetallic lanthanide complexes – pseudoenantiomeric 751 – structures of ligands 680, 685 BINOL–Zn(II) complexes 154 Bimetallic mechanism 682 BINOLAM ligand 267 (R)-BINAP•AgClO complex 1001 4 BINOLAM–Ti(IV) 774 BINAP•Ag(I) 992 Ti (µ-BINOLato) (µ -OH) 740 BINAP•AgF 1002 4 6 3 4 BINOLH BINOL–Ti catalyst 758 BINAP•AgOTf complex 994 8 (S)-BINPO 866 BINAP•AgPF 995 6 biomimetic transfer hydrogenation 94 BINAP/AgOTf/KF/18-crown-6 catalyst system Biphenylenediol 251 997 Bipyridine 611 1,1 -binaphthol 188 Binaphtholate yttrium aryl complexes 628 [3,5-bis(trifluoromethyl) phenyl]boronic acid BINOL 454, 457, 657, 658, 688, 723, 725, 190 741, 748, 1041 1,3-bis-exocylic dienes 230 – cross-linked polymer-supported 2,2’-bis(diphenylphosphanyl)biphenyl 872 1041 2,6-bis(2-oxazolinyl)phenylplatinum(II) – dendritic 1041 NCN–pincer complexes 871 – monoethers 454 Bis(2,6-diphenylphenoxide) aluminum triflimide 297 (R)-H8BINOL–Ti catalyst 732 (R)-BINOL 148, 170, 248, 277, 284, 334, 657, Bis(2-oxazolinyl)xanthene ligands 140 735, 741, 750 (R,R)-N,N -bis(3,5-di-tert-butylsalicylidene)- (R)-BINOL–Ti 758 1,2-cyclohexanediamine 162 i (R)-BINOL–Ti(O Pr)2/(R)-BINOL complex Bis(3-indolyl)methanes 837 750 Bis(4-substituted-2,6-di-tert-butylphenoxide) (R-BINOL–MgI2 catalyst 149 262 (S)-BINOL 322, 335, 454, 455, 664, 730, 871 Bis(amidate) complex 796 (S)-BINOL–Ti 730 Bis(boronic acid) 1028 (S)-H8BINOL 730 2,2-Bis(diphenylhydroxymethyl)binaphthyl F8BINOL 752, 787 87 H4BINOL/Ti/H4BINOL 759 Bis(indolyl)methanes 249, 410 H4BINOL/Ti/H8BINOL 759 Bis(iodomethyl)zinc 768 BINOL catalyst 259 Bis(organoaluminum) complex 264 1072 Index

Bis(oxazoline)s 136, 147, 169 Bisoxazolines 916, 1050 – tridentate 169 – supported on poly(ethylene glycol) Bis(oxazoline)s-MgI2 139 1050 Bis(oxazoline)s–Mg(NTf2)2 catalysts 141 Bisoxazoline copper(II) complexes 914, 916, Bis(oxazoline)s–Mg(OTf)2 144 978 Bis(oxazoline)s–MgI2 137 – chiral dendritic 916 Bis(perfluorobutanesulfonyl)amide 655 Bisoxazoline Cu(II) complexes 915 Bis(pinacolato)diboron 1021 – polymer-bound or dendritic 915 N,N-bis(siloxy)enamines 479 Bisoxazoline/copper(II) complexes 980 N,N-bis(trifluoromethanesulfonyl)- – spirocyclic 980 benzamidines 37 2,2-bispyrroles 502 – Hammett σp 37 1,3-bissiloxy-1,3-dienes 473 –pKa Value 37 Bisstannyl compounds 1027 Bis(trifluoromethanesulfonyl)amine 473 2,2-bisthiophenes 502 1,1-bis(triflyl)alkanes 41 N,O-bis(trimethylsilyl)hydroxylamine 942 –synthesis 41 Bithiophenes 438 Bis(triflyl)amide 303 BMPD-yttrium isopropoxide complex 628 Bis(trimethylsilyl)peroxide 528 Bolm’s system 164 2,2-bis(tritylamino)-4,4- C–F bond cleavage 241–244 dichlorobenzophenone 735 – activation through F–Al interaction Bis-1,2-(2,6-dihydroxyphenyl)ethane, 241–244 2-hexylresorcinol 599 Borate ester 234–235, 235 Bis-aluminated phenoxide 274 – cage-shaped 234 Bis-aluminated triflic amide 310 Boron Polymer 1020–1028 Bis-ferrocenyl amide phosphine 999 – Main-Chain 1026–1028 Bis-oxocane type compounds 205 – Side Chain 1020–1022 – synthesis 205 3,3 -Br2BINOL 8, 804, 832 Bis-phosphoramide 507 6,6 -Br2BINOL 748, 758, 832 Bis-silylated β-hydroxycarboxylic acid 494 Brassard’s diene 86, 761 Bis-sulfonamide catalyst 88 Brassard-type diene 953 Bis-thiourea catalysts 68 (R)-3,3 -Br2 –BINOL 153 – Axially chiral 68 (S)-6,6 -Br2BINOL 773 Bis-titanium isopropoxide 792 4-bromo-1-crotonoyl-3,5-dimethylpyrazole Bis-titanium(IV) catalyst 736 881 Bis-triflylamide 319 Bromo homoallylic alcohols 552 – C2-symmetric 319 α-bromoacrolein 876 Bis[(R)-1-phenylethyl]amine 487 2-bromoacrolein 190, 755 1,1-(2,2-bisacylamino)binaphthalene Bromobutyl boronate 1020 657 (+)-3-bromocamphor 324 Bisbenzimidazole 917 Bromohydrins 198 BisBINOL ligands 751 Bromohydroxylation 991 Bishomoallylic alcohols 610 – by silver(I) salts 991 β,β-bisindolyl ketones 592 Bromomethoxylation 991 1,3-bisindolyl compounds 393 – by silver(I) salts 991 Bismuth chloride 563 Bromopyridine 177 Bismuth nitrate 557 α-bromostyrene 179 Bismuth triflate 555 Bromothiophene 176 Bismuth(III) iodide 553 Brønsted acid 35, 46–50, 52–53, 56 bismuth(III) mandelate 576 – activation of electrophiles 56 Bismuth(III) nitrate pentahydrate 557 – as an Electron Acceptor 52–53 Bismuth(III) Salts 581 – as a Proton Donor 46–50 – in Ionic Liquids 581 – Brønsted–Lowry definition 35 Bismuth(III) Triflate 581 – intermolecular reaction 46–50 – polymer-supported 581 – Lewis definition 35 Index 1073

Brønsted acid catalysis 53, 62 C–H bond activation processes 223 Brønsted acid catalyst 89 – rhodium-catalyzed 223 – bearing bis(triflyl)methyl group 89 Ca(II) Lewis acids 135 Brønsted Acid-Assisted Chiral Brønsted Acid Ca(II)-catalysts 149 (BBA) 24–29 Camphorsulfonamide 729 Brønsted acid-assisted chiral Brønsted acid 10-camphorsulfonic acid 500 (chiral BBA) 29 (−)-Caparrapi oxide 21 – formation 29 Carbamate 991 Brønsted Acid-Assisted Chiral Lewis Acid Carbene Au(I) complexes 1004 (BLA) 1–12 Carbinols 262 – generation 3 – chemoselectivity 262 –use 3 – stereoselective synthesis with MAD Brønsted acid-assisted chiral Lewis acid 262 catalyst 190 Carbocycles 970 Bu2BOTf 213 • – five- or six-membered 970 s-Bu2Mg LiCl 179 5-endo-dig-carbocyclization 1005 Bu3SnF 541 t-Bu-BOX 970 Carbocyclization reactions 989 n-BuLi 128, 180 – Silver(I) salts 989 Carbodiimides 804 n-Bu2Mg 180 n-BuMgCl 180 – asymmetric polymerization 804 n-Bu3MgLi 176, 180 Carbometalation 361, 365, 848–851 • n-Bu3MgLi LiCl 180 – carbon–carbon triple bonds 365 3-buten-1-ol 615 Carbometalation reaction 368 3-((E)-2-butenoyl)-1,3-oxazolidin-2-one 615 – of phenols with chloroacetylene 368 3-(2-butenoyl)-1,3-oxazolidin-2-one 664 Carbomethoxylation 3-butenylmagnesium chloride 801 – of aliphatic amines 605 1-tert-butoxycarbonyl-2-(tert- Carbon Bond Forming Reactions 987–991 butyldimethylsiloxy)pyrrole 537 – Achiral Silver(I)-Catalyzed 987–991 tert–butyl–pybox complexes 879 Carbon–carbon bond formation 475 tert-butyl hydroperoxide 170, 782 – diastereo- and diastereoface-selective 1-butyl-2-propenyl vinyl ether 328 475 1-butyl-3-methylimidazolium chloride 247 Carbon–carbon bond-forming 2,6-di(t-butyl)-4-methylpyridine catalyst 357 – organosilicon Lewis acids promoted t-butyl isocyanide 508 503 n-butyl triflate 1004 Carbon–carbon bond-forming reactions 2,6-tert-butyl-4-methylpyridine 745 860–890, 1004–1011, 1035, 1040 Butylation 264 – Gold(I) and Gold(III)-Catalyzed – Al(III) Lewis Acids 264 1004–1011 Trans-tert-butylation reaction 247 – by Ti catalyst 1040 – of enamide compound 247 – transition-metal catalyzed 860–890 4-tert-butylcyclohexan-1-one 264 Carbon–carbon bonds 1010 1,2-bis(tert-butyldimethylsilyl)hydrazones – hydroamination of unsaturated 1010 603 t-butyldimethylsilyl enolate 487 Carbon–heteroatom bond-forming reaction N-tert-butyldimethylsilylhydrazones 603 891–897 Butyllithium 263 – transition-metal catalyzed 891–897 Tert-butylphenylketone 262 Carbonyl addition 260–277, 353, 494 3,5-di-tert-butylsalicylic acid 744 – Al(III) Lewis acids mediated 260–277 c – Ga(III) Lewis Acids Promoted 353 C–H activation processes 222–224 – intramolecular 494 – boron (III) Lewis acids catalyzed Carbonyl alkylation reaction 260 222–224 – organoaluminum complexes 260 1074 Index

Carbonyl allylation 215, 489 Cascade reaction 847 Carbonyl compounds 252, 253, 485–496, – of aldoxime 847 733, 771, 803, 1001 [Rh2(OAc)4] catalysis 608 – α-Amination 1001 Catalyst turnover frequency 676 – aldolization of α,β-unsaturated 252 Catalyst turnover number 676 – bis-silylation of α,β-unsaturated Catalytic asymmetric nitroaldol reaction 694 catalyzed by Pd(OAc)2 494 Catalytic Grignard Addition to Ketones – catalytic asymmetric epoxidation 687 181–182 – complexation of α,β-unsaturated 253 Catecholborane 170, 360 – cyanation 771 Catecholboronate 235 – direct asymmetric hydroxylation 803 Cationic zirconium complexes 841 – Hosomi–Sakurai allylation CbzNH2 52 489–490 Ce(III)[(R)-BNP]3 complex 662 – nucleophilic additions 490 Ce(NO3)6(NH4)2 662 – nucleophilic allylation 733 Centrolobine 431 –R3SiX-promoted reactions 485–496 (−)-centrolobine 564 – reactions with heteroatom Ceric ammonium nitrate 608 nucleophiles 493–496 Cetyltrimethylammonium bromide 160 Carbonyl group 25 6,6 -(CF3)2BINOL 749 – activation by TADDOL 25 6,6 -(C2F5)2BINOL 830 Carbonyl-ene cyclization 752 Chan’s diene 745 Carbonyl-ene reaction 258, 742, 747–752, Chelate controlled reactions 214–215 874, 884, 888 – boron (III) Lewis acids promoted –(S)-α-benzyloxypropanal with 214–215 2-methylprop-1-ene 742 Chelation control 386 – enantioselective by BINOL-based Chiral Al(salen)Cl complex 268 aluminum Lewis acid 258 Chiral Brønsted Acids 62–79 –ofchiralα-hydroxyaldehydes 742 Chiral Lewis acid catalysis 624 – of ethyl glyoxylate with α-methyl – in aqueous media 624 styrene 751 Chloral 277 – of formaldehyde, vinyl and alkynyl (−)-chloramphenicol 991 analogs of glyoxylates 752 α-chloro-α,β-cyclohexanone 626 – of glyoxylate 752 (Z)-chloro allylic alcohol 256 – of glyoxylate ester with olefins 749 2-chloro-2,3-epoxycarboxylic ester 280 – α-methylstyrene with glyoxylate 750 3-chloro-2,3-diarylpropanols 221 – of olefins and trifluoropyruvat 874 2-Chloroacetaldehyde dimethylacetal 473 – Ti catalyzed 747–752 Chloroacetylene trimethylsilylated 367 – with Pd catalysts and chirally flexible Chloroaluminate 283 phosphine ligands 888 N-(p-chlorobenzylene)aniline 882 – with methylenecyclohexane 884 Chlorodialkylboron Lewis acid 211 Carbonylation 227 Chlorodicyclohexyl borane 225 • –BF3 OEt2 and cobalt complex Chlorohydrin 198, 528, 570 catalyzed 227 – direct synthesis 528 carbopalladation 578 Chlorotitanium enolates 741 Carborane acid 43–45 Chlorotriethylsilylacetylene 358 –acidities 43 (−)-Chromazonarol 20 Carbosilane dendrimers 1028 Chrysene 349 P-carboxybenzaldehyde 647 Cinchona alkaloid derivative 616 Carboxylation 245 Cinchona alkaloid motif 75 – of fused aromatic compounds 245 Cinchona alkaloid-based ammonium salt Carreira’s catalyst 745 83 Caryophyllene 6 Cinchona alkaloids 930 Cascade Michael-aldol reaction 78 Cinchona-alkaloid catalyst 78 – of mercaptobenzaldehyde 78 Cinchonine 773 Index 1075

Cinnamic acid 60 – of Nitrogen Nucleophiles, Cu – reaction with benzene 60 catalyzed 942–943 cis-1,2,6-trimethylpiperidine 664 – stoichiometric enantioselective 147 cis-aziridine 879 Conjugate addition reactions 393 cis-carboxyethyl-1,3-diphenylaziridine 882 – catalyzed by InBr3 393 Citronellene 256 Conjugate Additions 686–687, 938–943 Claisen condensation reaction 832 – Lanthanide Lewis Acid promoted – α,α-disubstituted esters, catalyzed by 686–687 ZrCl4 832 – of Carbon Nucleophiles Cu catalyzed Claisen rearrangement 64, 207, 327–331, 938–942 568, 908–909, 1005 Conjugate base 36 – Al catalyzed 327–331 Conjugate-addition-initiated ring closure 555 – asymmetric enolate 331 Cooperative intermolecular catalysis 671 – Au catalyzed 1005 Cooperative intramolecular catalysis 671 – Bismuth (III) Lewis Acids 568 Coordination of Lewis acids 250–253 – Cu catalyzed 908–909 – models for 251 – enantioselective 207, 330 Copper acetylide 960 – of substituted allyl vinyl ethers 328 Copper Lewis acids 903, 904 – Common 904 – C2-symmetric bromoboron Lewis acid promotes 207 – Jahn–Teller effect 924 Claisen Rearrangement Reactions 147–148, Copper(I)–Fesulphos complex 925 Copper(II) triflate 1001 174–175 Corey lactone 320 – Zn(II)-catalyzed 174 Corey’s BLAs 3 (−)-clavosolide 494 Corey’s chiral BLAs 13 Cleavage reactions 231 Coupling of anilines 846 Cleaving reactions 891–897 – Zr-catalyzed three-component 846 – transition-metal catalyzed 891–897 Cp2YCl 626 Clerodane decalin core 28 + − CpFe (CO)P(OCH ) (THF)]BF 863 Clerodane diterpene 29 3 3 4 Cr complexes 878 Co–salen complex 865 Cr(salen) complexes 878 Cobalt–phosphine complexes 863 Cr–salen complexes 865 2,4,6-collidine 483 Cross aldol-Tishchenko reaction 703, 706 Combined acid catalysis 1–29, 2 – with Y-salen complex 706 – classifications 2 – yttrium-salen-complex-catalyzed Complexation asymmetric 703 – Lewis Acid Activation 361–369 Cross-aldol reaction 740, 916 Complexes 894 – of pyruvates catalyzed by Condensation 851 Cu(OTf)2/t-Bu-BOX 916 – Zr or Hf catalyzed 851 Cross-coupling reaction 226, 987, 1004 Condensation reaction 1011 – by Gold(I) and gold(III) compounds –NaAuCl4-catalyzed 1011 1004 Conia-ene reaction 1005 – iodobenzene and arylboronic acids Conjugate acid 36,45 1004 Conjugate addition 120–121, 145, 147, – palladium-catalyzed 226 641–644, 686, 687, 688, 942–943 – of thiopyridines 226 – Lewis acids 120–121 Crossed prins cyclization 431 – Lewis acid catalyzed 145 – catalyzed by InCl3 431 –ofcyanidetoα,β-unsaturated Crotonaldehyde 252 carboxylic acid derivatives 686 (E)-3-crotonoyloxazolidin-2-one 612 –ofcyanidetoα,β-unsaturated imides 3-crotonoyloxazolidinone 612 687 1-crotyl naphthyl 568 –ofcyanidetoβ-aryl, alkyl, and alkenyl Crotyl(vinyloxy)silanes 503 αβ-unsaturated N-acylpyrroles 688 Crotylation 10 1076 Index

Crotylboronates 451, 609 – (salen)AlCl complex 686 – In(OTf)3-catalyzed reaction 451 – lanthanide-PyBOX complex 686 Crotyldiisopropoxyboranes 8 Cyanation 650, 651, 649–651, 672, 676, Crotylgallium 353 768–777 Crotylsilane 992 – N-diphenylphosphinoylimine 676 Crotylstannane 383 – enantioselective of aldehydes 774 Crotyltrimethoxysilane 992 – lanthanide Lewis acid catalysis Cu(ClO4)2/C3-symmetric trisoxazoline 924 649–651 Cu(I) complexes 871 –ofacetophenone 672 Cu(II) bisoxazoline complexes 947 – of aldehydes and ketones catalyzed by – recycling 947 Yb(OTf)3 650 Cu(II) Schiff base complex 953 – of ketones catalyzed by Cu(II)/t-Bu-BOX 953 silylene-bridged Pr complex 651 Cu(II)/bisoxazoline complexes 905, 914 – Ti catalyzed 768–777 Cu(II)/BOX catalyst 953 Cyanation of ketones 391 Cu(II)/pybox complex 911 –InBr3 catalyzed 391 Cu(II)/salen complex 975 Cyanation reactions 593, 613 Cu(II)/trisoxazoline complexes 963 – scandium catalyzed 613 Cu(II)–chiral bisoxazoline complexes 903 Cyanide 390 Cu(II)–chiral bissulfoximine complexes – addition reaction 390 950 Cyanide transfer reaction 277 Cu(MeCN)4ClO4 964 Cyano-ethoxycarbonylation reactions 709 Cu(OTf)2 138 Cyanohydrin 651, 264, 267, 768, 770, 843 Cu(OTf)2 complexes 976 – from alkenes is Zr catalyzed 843 Cu(OTf)2/t-Bu-BOX 914, 924, 926, 944, 945, Cyanohydrin carbonate 772 956 Cyanohydrin formation 390 Cu(OTf)2/(phosphinophenyl)benzoxazine Cyanohydrin trimethylsilyl ether 73, 774, 775 950 Cyanosilylation 3, 673, 671–675, 774, 1041 Cu(OTf)2/bis(imine) 958 – catalytic asymmetric of aldehydes Cu(OTf)2/bisoxazoline 910 671 Cu(OTf)2/Bn-BOX 942, 976 – catalytic Enantioselective of Ketones Cu(OTf)2/BOX complexes 969 Using Gd Complex 673 Cu(OTf)2/diamine 937 – enantioselective 3 Cu(OTf)2/diamine catalyst 919, 921 – of aliphatic aldehydes Binol-Ti Cu(OTf)2/Ph-BOX 908, 930, 945, 970 supported 1041 Cu(OTf)2/t-Bu-bisoxazoline 905 – of Ketones with La catalysts 671–675 Cu(OTf)/Ph-BOX 958 Cyanosilylation reactions 264–271 Cu(PF6)(MeCN)4 958 – Al catalyzed 264–271 Cu(SbF6)2 968 – aluminum catalysts 266 Cu(SbF6)2/t-Bu-BOX 939, 944 Cyanotitanium 768 Cu(SbF6)2/Adam-BOX 945 Cyclic acetals 41 Cu(SbF6)2/BOX complexes 973 – preparation 41 Cu–HY/Ph-BOX 970 Cyclic amine 217 (−)-Cubebol 1008 Cyclic dienes 423 CuCl2/aza(bisoxazoline) 978 – imino Diels–Alder reaction 423 CuCl2/aza(Bn-BOX) 978 Cyclic diketones 974 CuF/bis(diphenylphospholane) complexes Cyclic enol ether 412 919 – reaction of pyrroles 412 CuI/l-proline 963 Cyclic ethers 476 Cumene hydroperoxide 148 Cyclization 20, 45, 115, 200, 440, 479, 481, Cumyl hydrogen peroxide 787 522–523, 530, 607, 851 Curtius rearrangement 686 –[2+ 2] 522 –(S,S)-ErCl3–PyBOX complex 686 – Acid catalyzed 45 –(S,S)-[(salen)Al]2O 686 – asymmetric 530 Index 1077

– catalyzed by In(OTf)3 440 – of nitrones catalyzed by chiral – cationic 115 bis-titanium catalyst 17 – destannylative 479 –Pd-catalyzed 382 – enantioselective polyene 530 – promoted by Yb(OTf)3/PyBOX 664 – endo-dig 851 –tandem[4+ 2]/[3 + 2] cycloaddition of –ofpolyene 20 nitrocyclopentene and vinyl ether – of reagent-controlled 324 diastereoselective polyene 22 –tandeminter[4+ 2]/intra[3 + 2]of silyl – oxocarbenium ions 481 tethered nitroalkene and chiral vinyl – regio and stereoselective 1,2, n-triols ether 324 200 – three-component 1,3-dipolar 653 α β – Sc(OTf)3-catalyzed, diastereoselective –using , -unsaturated 2-acyl imidazole 607 666 + –tandem[4+ 2]/[3 + 2] 522 [2 2] Cycloaddition 765–767 Cyclization reactions 877–890 – Ti catalyzed 765–767 – transition-metal catalyzed 877–890 Cycloaddition 1,3-dipolar 1043 Cycloaddition 16, 17, 312, 322, 324, 381, 382, – diphenyl nitron to vinyl ethers 1043 416, 428, 429, 493, 504, 653, 652–654, 664, Cycloaddition of 297 666, 667, 667, 764, 847, 848, 944, 953, 966, – Al catalyst 297 968, 969, 999 Cycloaddition reaction 5, 140–141, 151–153, –[2+ 2 + 2] 302 188–195, 295–327, 304–331, 421–427, 492–493, 753–768, 958–970 –[2+ 3], Zr catalyzed 848 –[2+ 1] 295 –[2+ 3],Hf catalyzed 847 –[2+ 2] 295 –[3+ 2] 302, 493 –[4+ 2] 304–327 –[4+ 2] 312, 322, 324 – Al catalyzed 327–331 –[4+ 3] 312 – B(III) catalyzed 188–195 – 1,3-dipolar catalyzed by InCl 429 3 –[3+ 2], [2 + 2], and [4 + 3] cu – 2-methoxycarbonyl-2-cyclopenten- catalyzed 958–970 1-one 968 – of 2,3-dihydrofuran with – Azomethine ylides 999 1,4-benzoquinones using a chiral BLA – between diazoacetates and 5 α-substituted acroleins 16 – In(III) salts catalyzed 421 – catalyzed by In(OTf)3 416 – silicon catalyzed 492–493 – catalyzed by InCl3 428 – Ti catalyzed 753–768 + – enantioselective [3 2], Si(IV) Lewis – Zn(II)-Catalyzed 151–175 acid catalyzed 504 Cycloaddition, 1,3-dipolar 874–877, 876, – endo and exo selective 966 878, 884, 958, 964 – In(III) catalyzed 381 – Cu(II)-catalyzed 958 + – intramolecular [2 3] 847 – Fe complex catalyzed 876 + – intramolecular [3 2] 324 – of ary imines with dipolarophiles – lanthanide Lewis acid catalyzed 884 652–654 – of azomethine ylides with – of carbonyl ylide 667 electron-deficient alkenes 964 – of carbonyl ylide promoted by – of nitrones with α,β-unsaturated Yb(OTf)3/PyBOX 667 aldehydes 874 – of cyclopentadiene to pyrazolidinone – Rh or lr catalyzed 878 crotonate 944 – transition-metal catalyzed 874–877 –ofDanishefskysdienetoN-tosyl Cycloaddition 196–197, 201–202, 517–522, imines 953 614–615, 663, 665, 844–848, 951, 966 – of diazoacetates to acroleins 764 –[3+ 2] 197 – of diene cu catalyzed 953 –[3+ 3] 196 – of nitrogen-stabilized oxyallyl cations –[4+ 3] 197 with dienes 969 – 1,3-dipolar 614–615 1078 Index

Cycloaddition (contd.) 1,3-cyclopentadiene 492 – B(III) catalyzed 196 Cyclopentadienyl dicarbonyl iron Lewis acid – between dienes and α,β-unsaturated 879 1-acyl-3,5-dimethylpyrazoles 951 Cyclopentadienyl zirconium complexes 855 – catalytic asymmetric 1,3-dipolar Cyclopentane 801, 1006 663–667 – by gold-catalyzed carbocyclization – catalytic asymmetric 1,3-dipolar 665 reactions 1006 – hetero [2 + 2] 201–202 Cyclopentanone-2-carboxylic acid tert-butyl – In(acac)3 381 ester 999 – of 3-oxopyrazolinin-1-ium-2-ides 966 Cyclopropanation 767–768, 1050 – of azomethine imines with terminal – of diphenylethylene 1050 alkynes 966 – Ti catalyzed 767–768 – pericyclic 844–848 Cyclopropanation reaction 1006 – scandium and yttrium catalysts – Au catalyzed 1006 614–615 Cyclopropanes 493 – Sn-compounds catalyzed 517–522 Cyclopropyl carbinols 452 [3+2] Cycloadditions 763–765 – rearrangement 452 – Ti catalyzed 763–765 (RRu)-[(p-cymene)RuCl(S)-BINPO] SbF6 866 Cycloalkenones 424 [(p-cymene)RuCl(R)-QUINAP] SbF6 866 –InCl3 catalyzed reaction 424 [(p-cymene)RuCl(S)-TolBINPO] SbF6 866 Cyclobutane 426, 1006 –[3+ 2] cycloaddition 426 d Cyclobutane derivatives 765 α-D-ribofuranosides 117 Cyclobutanone 843 – stereocontrolled synthesis 117 Cyclocondensations 757 D-glucal 452 – activated dienes with aldehydes 757 Dactylolide 430 Cyclohexadiene 195 Danishefski’s diene 322 – chemoselective diels alder reaction –[4+ 2] cycloaddition 322 195 Danishefsky’s diene 88, 154, 191, 234, 422, 1,3-cyclohexadiene 492 595, 602, 845, 953, 998 (1R,2R)-cyclohexane bis-sulfonamide 295 – dimethyl-substituted 953 Trans-cyclohexane chlorohydrin 283 Danishefsky-type dienes 869 Cyclohexane-1,4-dione 264 DBFOX–Ph ligand 875 Cyclohexanecarboxaldehyde 263 Deacetalization 892 1,3-cyclohexanedione 881 – by transition-metal catalysts 892 Cyclohexanone enolates 366 1-Decene 850 – ethenylation 366 n-decylaluminum 850 Cyclohexanones 553 Dendralene 304 – 1,2-Allylation 553 Dendrimers 1028 (R,R)-cyclohexene-1,2-diamine 770 Denishefsky’s diene 757, 758 Meso-cyclohexene oxide 283 (−)-11-Deoxytaondiol methyl ether 20 Cyclohexene oxide 285, 682 Deprotection 502, 854, 935 – kinetic resolution of one-substituted –byZrCl4 and NaBH4 854 285 – of prenyl esters 502 Cyclohexenone 333 – of propargyl amines 935 Cycloimines 799 Desilylation 854 Cycloisomerization 1006 – Zr catalyst 854 – Au catalyzed 1006 rac-Desoxyequilenin 1008 – of enynes 437 2,6-di-tert-butylpyridine 499 Cyclopentadiene 64, 188, 219, 308, 755 Di(i-propoxy)titanium dichloride 742 – A reaction Al catalyzed 308 Di-µ-oxo titanium–salalen complex 784 – Aluminum Lewis acid-catalyzed DA (R,R)-di-µ-oxo salen–Ti complexes 790 reaction 306 3,5-di-tert-butyl-2-hydroxybenzaldehyde – reaction with acrolein 64 770 Index 1079

β,β-dialkyl-γ-substituted pantolactones Diels–Alder cycloadducts 950 607 – diastereo- and enantioselective 950 N,N-dialkylanilines 781 Diels–alder dimerization reaction 863 – Asymmetric FC reaction 781 – cobalt–phosphine-catalyzed Dialkylzincs 497 intermolecular 863 2,2-diallyl-2,3-dihydronaphthalene-1,4-dione Diels–Alder reaction 3, 13, 26, 32, 53, 55, 64, 568 82, 85, 88, 110, 112–115, 142, 190, 190, 191, Diallylisopropylsilane 218 192, 188–195, 196, 297, 304–322, 325, 421, – michael addition 218 421–425, 426, 492, 493, 519, 520, 560–562, Diamines 171 594–597, 613–614, 625, 652, 652, 653, 653, 1,2-diamines 685 657, 658, 659, 656–663, 753–756, 844, 845, Diaminochlorophosphine 349 861–874, 945, 948, 951, 978, 1034, 1040, 1,2-diaminocyclohexane 723 1046 α α β , -Diaryl -amino alcohol 1023 – activated 1,3-dienes 492 gem-diarylethylene 837 – Al(III) Lewis acids mediated Diarylmethanes 413 304–322 – synthesis catalyzed by InCl3 413 – aminosiloxydiene and aldehydes 26 Diarylmethylamines 163 – between acroleins and 1,3-diaryloxy-2-propanols 571 cyclopentadiene 864 Diarylpiperidones 60 – between acrylonitrile and Diarylpropene 835 cyclopentadiene 871 Diarylzinc 731 – between acryloyl-N-oxazolidinones Diazaaluminolidine 320 and cyclopentadiene 871 Diazocarbonyl 426 – between 2-bromoacrolein and – intermolecular 1,3-dipolar dienophiles 190 cycloaddition 426 – between cyclopentadiene and α-Diazocarbonyl compounds 451 acryloyl-2-oxazolidinone substrates –InCl-catalyzed reactions 451 3 948 – In(OTf) -catalyzed intramolecular 3 – between cyclopentadiene and insertion 452 3-crotonoyl-1,3-oxazolin-2-one 1046 DIBAL reduction 262 – Bismuth (III) Lewis Acids 560–562 N,N-dibenzyl-aminoaldehyde 119 –BLAcatalysts 191 Dibenzyl azodicarboxylate 973, 974, 1001 Dibenzylamine 932 – boron Lewis acid catalyzed 188–193 2,5-dibenzylcyclopentanone 357 – 2-bromoacrolein with methyl Dibromo-boron type catalyst 188 butadiene 755 1,2-dibromoethane 987 – catalytic asymmetric 315, 656–663, 2,3-dibromopropene 552 658 2,6-dibromopyridine 177 – catalytic asymmetric inverse-electron Dicationic Carbonyl Compound 58 659 Dichloro(4-methylphenyl)iodine 790 – Catalytic asymmetric promoted by Dichlorogallium hydride 372 chiral Yb catalysts 657 Dichloromalonate ester 832 – catalyzed by LLA 13 Dichlorophenylborane 221 – chiral BLAs for 3 Dichlorophosphetidine 348–349 – chiral boron catalysts 190 Diels–Alder 505, 947 – chiral 1-cinnamoyl sulfinylpyrrolidine – of 3-acryloyl-oxazolidin-2-one 947 with cyclopentadiene 308 – of methacrolein with cyclopentadiene – chemoselective 55, 195 505 – Cu(II)-catalyzed enantioselective 945 Diels–Alder cycloaddition 517, 867, 943–952 – Cu(II)/bisoxazoline-catalyzed 978 – Cu catalyzed 943–952 –1,3-cyclohexadieneB(C6F5)4 catalyzed – of cyclopentadiene and methacrolein 493 867 – cyclopentadiene with acrolein – Sn-compounds catalyzed 517 derivatives 755 1080 Index

Diels–Alder reaction (contd.) – of cyclopentadiene and methyl – cyclopentadiene with 3-acryloyl- or methacrylate 1040 3-crotonoyloxazolidinones 614 – of cyclopentadiene with a chiral – cyclopentadiene with spirodione 625 3-acryloyl-1,3-oxazolidin-2-one 614 – of cyclopentadiene with azachalcones –Danishefsky’sdiene 88 951 – Danishefski’s diene and aldehydes – of cyclopentadiene with 322 N-acryloyl-oxazolidinone 871 – diastereoselective 519 – of cyclopentadiene with acryloyl 870 – diastereoselective using chiral – of diene with crotonaldehyde and auxiliary 307 acrolein 863 – diene with aldehyde 191 – of 1,3-dienes with olefins, Zr or Hf – dienyl alcohol and α-acetoxyacrolein catalyzed 844 304 – of dimethyl fumarate with – effect of coordination of Lewis and cyclopentadiene 306 – of ester-tethered substrates 309 Brønsted acids on chemoselectivity – of furan 844 196 – of isoprene and methyl vinyl ketone – effects of metals salts on the rate 110 595 – enantioselective 188, 520 – of lactones with cyclopentadiene 311 – enantioselective inverse-electron – of maleimide 320 demand 659 – of methyl crononate and – enantioselective with amidinium salt cyclopentadiene 190 catalysts 82 –ofα-methyl-α,β-unsaturated ketones – exo-selective 308 with cyclopentadiene 308 – exo selective asymmetric 519 – of nitroalkene MAPh promoted 325 – fumaroyl–oxazolidinones 870 – of nonactivated conjugated dienes – In(III) salts catalyzed 421 872 –InCl catalyzed imino 423 3 – of oxazoline 754 – In(OTf)3 catalyzed intramolecular –of8-phenylmenthylα-fluoroacrylate 422 306 – intramolecular imino 426 – of silyloxydiene and aldehydes 652 –ionic 421 – of sterically hindered dienophiles – methacrolein with 1,3-dienol 309 derivatives 756 – of thiabutadiene and electron-deficient – of acrylates with cyclopentadiene 317 olefin 653 – of acrylates with 2-siloxy-1,3-butadiene – of thiabutadiene catalyzed by Yb(OTf)3 297 653 –ofN-acryloyl and N-crotonoyl – of 1,2,3-triazole with dimethyl oxazolidinones 319 acetylenedicarboxylate 1034 – of acryloyl oxazolidinones mediated by – of various α,beta-unsaturated Et2AlCl 305 carbonyls 309 – of activated carbonyls 322 – point binding model 192 – of allylic alcohol and dienyl alcohol – promoted by LPDE 112–115 304 – proposed mechanism for the InCl3 – of an achiral dienophile with catalyzed imino 425 cyclopentadiene 315 – quinone 660 – of an acrolein and cyclopentadiene – reversal of chemoselectivity 53 866 – scandium complex with –ofazadiene 424 ferrocenyl-based chiral diol ligand – of chiral substrates 194–195 613 – of coumarin with isoprene 845 – Sc salt catalysts 594 – of cyclic diene and glyoxalate 874 – Super BLA for selective 32 – of cyclopentadiene 754 – TADDOL catalysed 85 Index 1081

– Ti catalyzed 753–756 3,4-dihydropyrimidin-2(1H)-ones 557 – transition-metal catalyzed 861–874 Dihydropyrimidinones 557 – with crotonoyl 870 3,4-dihydroquinoline-2-one 565 – with bis(oxazoline)s–Mg(II)complexes Dihydroxy bis(sulfonamide) ligand 729 142 3,3-diindoylmethane 410 – Yb(OTf)3 catalyzed under high 2,6-Diisopropylphenol 6 pressure 652 1,3-diketone 196, 975, 988 Diels–Alder reaction promoted 660 – cycloaddition 196 – catalytic asymmetric quinone 660 β-diketones 1004 Diels–Alder type reaction 89 – intermolecular addition 1004 – of diene with nitrosobenzene 89 1,3-dimethoxy-benzene 249 1,3-diene 580, 792 2,4-dimethoxy-2-methylbenzopyrans 602 – catalytic hydrosilylation 792 3,5-dimethoxy-2-hydroxy acetophenone 567 – intermolecular hydroamination 580 2,6-dimethoxyphenyl acetate 567 Dienynes 1007 2,2-dimethoxypropane 602, 617 – intramolecular cyclopropanation 2,2-dimethyl-1,3-dioxolanes 521 1007 Diethoxymethane 599 1,4-dimethyl-2,5-piperazinedione 264 3,3-dimethyl-1,2,4-butanetriol 774 Diethyl azodicarboxylate 405 Diethylzinc 723 4,4 -dimethyl-2,2 -bipyridine 951 Diethylzinc addition to imines 163 4-N,N-dimethylaminomandelic acid ethyl Diethynylvinylmethane 364 ester 781 Difluoroalkane 243 N,N-dimethylaniline 248, 916 α,α-difluoroenol silyl ether 636 Dimethyldioxolane 826 β,β-difluorohomopropargyl alcohols 647 1,3-dimethylindole 602 Difluoromethylene ketones 636 Dimethylmaleate 999 Difluoropropargyl bromide 647 2,6-dimethylphenol 676 Difluorovinyl allyl ethers 207 2,5-dimethylpyrrole 798 – enantioselective rearrangement 207 Dimethyltitanocene 794 (R)-DIFLUORPHOS 992 Diol Catalysts 83–89 gem-dihalocyclopropanes 989 Diols 574 – electrocyclic ring opening 989 – protection 574 1,2-dihydroisoquinoline 440, 990 Dioxepanes 481 2,3-dihydro-4H-pyran-4-one 757 1,3-dioxolanes 575 3,4-dihydro-(2H)-pyran 497 Dioxomolybdenum-N-ethylephedrine complex 3,4-dihydro-2H-pyran 423 782 Dihydrobenzofuran 426, 766 Diphenols 574 –[3+ 2] cycloaddition 426 – protection 574 2,3-dihydrofuran 426 α,α-Diphenyl-L-prolinol derivatives 1024 Dihydrofurans 387 1,3-diphenyl-1,3-propanedione 1005 –InCl catalyzed allylation 387 3 2,2-diphenyl-4-hexen-1-ol 990 Dihydrogen trifluoride tetrabutylammonium Diphenyl diselenides 449 842 Dihydroisoquinoline 68 – coupling reactions 449 1,2-dihydroisoquinoline derivative 990 (R,R)-diphenylethane-1,2-diol 787 5,6-dihydropyran-2-ones 487 1,2-diphenylethylene-1,2-diamine 770 Dihydropyrancarboxamides 953 Diphenylethylenediamine 159 Dihydropyranones 195 (R,R)-1,2-diphenylethylenediamine 879 – cycloadditions Lewis acid promoted Diphenylmethanol 244 195 Diphenylmethylsulfides 244 Dihydropyrans 387 N-Diphenylphosphinoyl 156 –InCl3 catalyzed allylation 387 1,1-diphenylpropene 837 Dihydropyridines 495 Dipyrrolyl alkanes 412 Dihydropyridone 845 – meso-substituted 412 1082 Index

Dipyrromethane 411 – lanthanide Lewis acid catalyzed – synthesis catalyzed by InCl3 or TFA 644–645 411 – of glyoxylate catalyzed by Yb(OTf)3 Direct aldol reaction 143, 156, 702–706, 705 645 – by chiral Mg(II) complexes 143 –ofα-methylstyrene with ethyl – lanthanide catalyzed 702–706 glyoxylate 1050 – of methyl ketones and hydroxyketones – scandium and yttrium catalyzed promoted by (S)-LLB-KOH 705 608–609 Direct Henry reactions 160 1,6-ene-ynamides 1006 – use of discrete Lewis acids and Enecarbamate 94, 412, 914, 1001 Brønsted bases 160 – reaction of pyrroles 412 Direct Mannich reaction 93 Enol ester epoxide rearrangement 779 – of 1,3-diketone with N-Boc aldimines Enol ester epoxides 778 93 – kinetic resolution of racemic 778 Dirhodium(II) carboxamidate 867, 868 Enol silanes 912 Dirhodium(II) carboxylates 867 – addition reaction, Cu catalyzed 912 Disilver(I) complex is 991 Enolsilylacetal 743 Disilyl cation 501 Enolsilylethers 636 α,α-disubstituted β-ketoester 832 – hydroxymethylation 636 2,6-disubstituted tetrahydropyrans 206 Enolates 359, 367, 704 1,3-dithiane 575, 603 – aldol-type addition and direct reaction Dithioacetalization 1032 704 – of carbonyl compounds 1032 – alkylation 367 1,3-dithiolanes 443 – kinetic 359 Divinyl ketones 972 Enolization 357 – asymmetric Nazarov cyclization 972 – Lewis acid activated 357 divinylbenzene 1048 Enones 392, 395, 397, 709 Diyne 363 – addition of allyltrimethylsilane to 1,4-diynes 364 395 Domino Diels–Alder/Prins/Pinacol reactions – addition reactions 397, 709 521 – additions catalyzed by InCl3 392 Dorzolamide 612 – catalytic asymmetric epoxidation 688 Drierite 654 N-enoyl-4-phenyl-1,3-oxazolidinones 610 DTBM–SEGPHOS•Au(I) complex 1006 1,4-enyne 364 Enynes 437, 439, 1007, 1008 e – cycloisomerization 1008 Electrophilic additions 565–567 – intramolecular cyclization 439 Electrophilic amination 81 – intramolecular cyclopropanation Enamidomalonates 147 1007 β-enamidomalonates 939 –PtCl2-catalyzed cycloisomerization – Cu(II)-catalyzed addition reaction 437 939 (+)-8-Epi-puupehedione 20 Enamine 435, 793 (+)-epiaustralin 324 –InCl3 catalyzed 435 (+)-8-Epicaparrapi oxide 21 Enamine formation 453 (±)-epilupinine 627 – hydrogenation 793 Epimerization 431 –InBr3-catalyzed 453 Epothilones 703 Enantioselective reduction 144 Epoxidation 170, 687, 689, 690, 691, 692, – of trifluoromethyl ketones 144 782–786, 855, 895 Enantioswitching 659 – allylic alcohols using metallocene 5-endo-dig cyclization 798 catalysts 855 Ene reaction 608–609, 644–645, 645, – asymmetric 784 970–972, 1050 – BINOL–Zn(II) catalyst 170 – copper-catalyzed 970 – enantioselective 170 Index 1083

–ofα,β-unsaturated amides 692 – ring-opening reactions have been Al –ofα,β-unsaturated carbonyl mediated 280 compounds 687 – thiolysis 571–572 –ofN-acylpyrroles and transformation of Epoxides 453 of N-acylpyrrole unit 691 –InBr3-orInCl3-catalyzed conversion – of benzaldehyde with 453 phenyldiazomethane 895 1,2-epoxides 778 – of enones using La complex 690 – regioselective ring-opening 778 – of enones using La-BINOL 689 – Ti catalyzed 777–779 – of olefins with peracids or 2,3-epoxy alcohol derivatives 526 hydroperoxides 782 2,3-epoxy alcohols 203, 594 – postulatedx mechanism of Epoxy azide 527 lanthanide-catalyzed 689 Epoxy ester 856 – Ti catalyzed 782–786 – ring-opening fluorination of 594 Epoxide opening reactions 224 α,β-epoxycarboxylic acids 401 – boron (III) Lewis acids catalyzed 1,2-epoxycyclohexanes 224 224 Epoxyquinols 844 Epoxide rearrangement 122, 123, 449 Epoxytwinol 844 –InCl3-catalyzed 449 Erker’s catalyst 327 –LiBF4, promoted 123 Ester condensation 853 – LiBr promoted 123 – Hf catalyzed 853 – with LiClO4 122 Ester formation 546–549 Epoxide ring opening 205, 401, 402, 454, Esterification 57 777–779 – of carboxylic acids and alcohols 57 • –BF3 OEt2-promoted 205 Esterification reaction 174 – catalyzed by InCl3 402 – Zn(II)-catalyzed 174 – In and Ga monoether BINOL Esters 83, 193, 499–502 complexes catalyzed 454 – catalyst for 193 – regioselective 401 – enantioselective synthesis from Epoxide-opening process 693 ketenes 83 – One-pot sequential catalytic –R3SiX-promoted reactions 499–502 asymmetric epoxidation-regioselective (+)-Estrone 693 – enantioselective syntheses 4 Epoxides 203–205, 280, 404, 499, 526–527, Et2Zn 153, 156, 163 569–572, 593, 613, 681, 777, 841, 856, – second-generation 156 893 Et2Zn/(S,S)-linked BINOL 154 – alcoholysis 571 1,2-ethanethiol 444 – aminolysis 569–570 Ethenylation 366 – catalytic asymmetric ring opening – Ga(III) Lewis Acids promoted 366 681 Ethers 499–502, 891 – deoxygenation by Zr 856 – cleavage of 891 – desymmetrization 777 –Rg3SiX-promoted reactions 499–502 – intramolecular reaction 499 Ethoxyvinyllithium–HMPA system 127 – meso 613, 777 1-ethyl-3-methylimidazolium – opening of meso 570 trifluorosulfonylimide 888 – reaction catalyzed by InCl3 404 2-ethyl-1-hexene 793 – reaction of Nitriles with 570 – hydrogenation 793 – reaction with aromatic or aliphatic Ethyl cyanoformate 773, 773 amines 593 Ethyl diazoacetate 880 – rearrangement 203–205, 569 Ethyl glyoxylate 322, 781, 905, 970 – ring opening transition-metal – asymmetric FC reaction 781 catalyzed 893 Ethyl vinyl ketone 55 – ring opening, Zr catalyzed 841 – Diels-Alder reaction 55 – ring-opening reaction of 526–527 Ethylene glycol diethyl ether 1001 1084 Index

Ethynilation 4-fluorobenzenesulfonyl chloride 409 – Lewis acid activated 367 Fluoroborane Trip2BF 1021 1-ethynyl-2-propenyl pivaloates 1007 Fluorous catalysts 41 o-Ethynylanilines 368 (R)-fluoxetine 691 Ethynylgallium 365 Formaldehyde 256 • EtMe2MgLi LiCl 181 Fostriecin 705, 992 Etter’s urea 65 Friedel–craft type cyclization 202 Exchange reaction 175–179 – 2-arylthio-ketones 202 – with Zn(II) ate complexes 175 Friedel–Crafts acylation 357, 408, 834, 1038 – Br/Mg 179 – of anisol 1038 – halogen-magnesium 177, 176 – of anisole 408 – halogen-zinc 175 – of aromatic rings 834 – I/Br–Mg 178 – of 2-methoxynaphthalene 408 3-exomethylene β-lactam 963 Friedel–Crafts addition 391 – In(OTf)3 catalyzed 391 f Friedel–Crafts alkenylation 598 Febrifugine 620 – of arenes with alkynes 598 FeCl2/pybox complexes 897 Friedel–Crafts alkylation 74, 349, 373, 598, Felkin-Ahn-like cyclic transition-state model 618–619, 906, 907 743 – by scandium and yttrium 618–619 Ferrier reaction 206–207, 559 – Cu catalyzed 906 – boron (III) Lewis acids promoted – of aromatic compounds 598 206–207 – of indoles 74, 618, 907 – by bismuth trichloride 559 –ofα,β-unsaturated 2-acyl imidazoles Ferrier Rearrangement 419, 420, 437, 618 569 – reductive 373 –BiCl3 catalysed 569 Friedel–Crafts benzylation 599 – catalyzed by InBr3 420 Friedel–Crafts phenethylation 599 – catalyzed by InCl3 420 Friedel–Crafts reaction 173, 230, 245–250, – In(III) Lewis acid induced 437 655, 780–781, 834–838, 835, 837, 905–908, Ferrocene 837 906, 907 Ferrocene-dihydropyrimidinones 433 – Al(III) catalyzed 245–250 Ferrocenyl diazides 620 – boron (III) Lewis acid catalyzed 230 Ferrocenylborane polymers 1028 – catalytic asymmetric 780 1,2-ferrocenyldiamine 419 – catalyzed by Yb catalyst 655 FERRODIOL 613 – copper catalyzed 905–908 Fesulphos ligand 964,871 – dehydroxylative catalyzed by HfCl4 Fischer cyclization 798 835 Flavanones 395, 443, 563–564 – indoles with trifluoro ethylpyruvate – isomerisation of 907 2-hydroxy-substituted chalcones – of aromatic and heteroaromatic 563–564 compounds 906 – oxidation 395 – of benzene rings Hf-catalyzed 835 Flavones 395 – of indoles and arylidene malonates Fluoral-ene reaction 751 907 9-fluorenylmethylphenylsilylene 651 – regioselective, Zr and Hf catalyzed Fluorinated alkynylamines 220 837 1-fluoro-pyridinium triflate 619 – Ti catalyzed 780–781 4-fluoro-1,2-dihydronaphthalenes 490 –tandem α-fluoroacrylates 311 carboalkoxylation-friedel–crafts Z-fluoroalkene 243 alkylation 655 2-fluorobenzaldehyde 261 –Zr(Iv)andHf(IV)LewisAcids 4-fluorobenzaldehyde 261 Catalyzed 834–838 N-fluorobenzenesulfonimide 975 – Zn(II)-catalyzed 173 Index 1085

Friedel–Crafts sulfonylation 248 – corey’s BLAs 4 – of benzene 248 – enantioselective syntheses 4 Friedel–Crafts type addition 68, 93 Geranyl pyrrolidine 175 –ofindole 68 Glaser oxidative coupling 963 Friedel–Crafts type cyclodehydration 58 Glycine alkyl ester 152 Friedel–Crafts type reaction 280, 406, Glycine-derived silyl enolates 828 598–599, 622 Glycopyranosides 559 – In(OTf)3-catalyzed 406 – synthesis of 2,3-unsaturated 559 – of aromatic compounds 622 Glycosidation 117, 483 – of propylene oxide with cyclic/acyclic – oxygen and nitrogen nucleophiles alkenes 280 483 – scandium and yttirum catalyzed – with Lewis acids 117 598–599 Glycosides 469 Friedel–crafts/aldehyde cyclotrimerization Glycosyl N-phenyltrifluoroacetimidate 654 885 Glycosyl trichloroacetimidates 483 Fries rearrangement 567 Glycosyl trichloroacetylcarbamates 483 – Al catalyzed 246 Glycosylation 654, 654, 654 • – catalyzed by Bi(OTf)3 xH2O 567 – catalyzed by lanthanide triflate 654 Fullerene epoxide 224 – glycosyl fluoride catalyzed by Furan diol 452 lanthanide triflate 654 –chiral 452 – lanthanide Lewis acid promoted 654 Furans 218, 1009 Glyoxal bis-hydrazone 950 – gold-catalyzed cycloisomerization Glyoxylate 758 1009 Glyoxylate esters 912 Furo[2,3:5,6] Pyrano [4,3-b] Quinoline 560 Glyoxylate-ene reaction 752, 972 Furyl acrylamide 307 – enantioselective Cu catalyzed 972 Furyl hydroperoxides 786 N-glyoxyloyl camphorpyrazolidinone 609 Gold(III) porphyrin complexes 1010 g Grignard reagent 135, 147, 179, 181, 1027 Gallium(III) Lewis acid 347, 348, 351, 357, – bifunctional 1027 359, 361 Griseofulvin 611 – acidic tetracoordinated basic 370 Guanidine 80, 81, 581 – asymmetric catalysis 360 – axially chiral 81 – ligands 357 – chiral seven-membered 81 – organohalogen compounds 348–350 – C2-symmetric 80 – organometallic compounds 359–361 – C2-symmetric bicyclic 81 – organooxygen and organosulfur – polysubstituted 581 compounds 351–353 Guanidium Salts 80–81 – pentacoordinate 351 Guindon’s stereoselective defunctionalization – transition metal complexes 361 542 Gallium enolate 357, 365 (−)-Gymnodimine 945 Gallium phenoxide 368 Gallium tris(trifluoromethanesulfonate) 349 h Gallium(III) complexes 359 H–ZSM-5 zeolite 409 Gallium(III) halide 355 Hafnium triflate 834 Gallium-cobalt phenoxides 360 Hafnium(IV) perfluorooctane sulfonylamide Gallium-titanium phenoxides 360 852 Gallium/lithium/bis(binaphthoxide) catalyst Halide-PyBOX complex 680 360 Halides 499–502 Gas-phase aciditiy 37 –R3SiX-promoted reactions 499–502 Gd(O–iPr)3 671, 674, 684 Halofurans 1010 Gd(OTf)3 –PyBOX complexes 660 Halogenation 790, 973–976 Gem-diacetates 389 – Cu catalyzed 973–976 Georgyone – Ti catalyzed 757–764, 790 1086 Index

Halohydrin reaction 991 – of keto esters 662 Halohydrins 443 –SnCl4-Catalyzed 520 – reductive elimination 443 – Zn(II) catalyzed 153 Halosilanes 479 – Ti catalyzed 756–763 4-Halotetrahydropyrans 479 – Zr catalysts for 845 Halpgenation 581 Hetero Michael addition 53, 54 Hamett acidity function 36 Heterobimetallic lanthanide complexes 695 Hantzsch dihydropyridines 604 Heterobimetallic lanthanide–alkali metal Hantzsch ester 94, 976 complexes 695 HAuCl4 catalyst 1004 Heterobimetallic lanthanide–alkali Heck cyclization 553 metal–BINOL complexes, 695 Henry reaction 77, 79 Heterobimetallic Sc complex 676 – catalyzed by a novel cinchona alkaloid Heterocyclization 988 77 – gold(I)-catalyzed 988 – β-Nitroamine with high Heteropolymetalic catalyst 703 enantioselectivity 79 Hexadentate chiral ligand 670 Hepta-4,5-dienylamine 800 Hexafluoro-2-propanol 939, 975 – ring-closing reaction 800 Hexafluoroisopropanol 907 3,6-Heptadienyl ethers 478 Hexamethyldisilazane 625 Hetero Diels–Alder reaction 84, 86, 110, 1,1,1,3,3,3-Hexamethyldisilazane 446 112, 114, 153–154, 322–327, 520–521, 661, Hexamethyldisiloxane 654 662, 656, 656–663, 744, 756–763, 845, 865, Hexamethylphosphoramide 64 953–958, 998 1,5-Hexandiyne 798 – asymmetric catalysis 757 Hf(IV) Lewis Acids 825 – 1,3-Cyclohexadiene with N-Sulfinyl Hf(OTf)4 832 dienophiles 763 Hf(OTf)3 436 – enantioselective inverse HfCl4(thf)2 catalysts 852 electron-demand 761 HfCl4 835 • – 1-Methoxydienes with glyoxylate 757 HfOCl2 8H2O 852 – Ti catalyzed 744 Hoffmann camphor-based allylboronates Hetero Diels–Alder 86 609 – Ag catalyzed 998 Hofmann–Martius rearrangement 50 – Al catalyzed 322–327 Homo Mannich-Type reactions 556 – Asymmetric catalyzed by chiral Yb(III) – Bismuth (III) Lewis Acids 556 phosphate 661 Homo-aldol reaction 916 –BAMOLcatalysed 86 – of ethylpyruvate 916 – Bismuth (III) Lewis Acids 560–562 Homoallenic alcohols 1005 – catalytic asymmetric 656–663 Homoallyl alcohol 353, 840 – catalytic asymmetric promoted by – cleavage 353 Eu(hfc)3 656 Homoallyl ethers 476 – catalyzed by LiClO4 110 – tandem acetalization–allylation – cu catalyzed 953–958 reaction 476 – diastereo- and enantioselective 953 Homoallylgallium reagent 372 – effects of metals salts on the rate of Homoallylic alcohol 451, 734 110 – kinetic two-substituted 451 – mediated by alkali metal Lewis acid Homoallylic alcohols 218, 429, 431, 449, 450, 114 609, 732, 747, 890 – of aminodiene with aldehyde 84 – In(OTf)3-Catalyzed rearrangement – of aromatic aldehyde 86 450 –ofN-Arylimines 561 – linear 449 – of benzaldehyde 324 – prins cyclization 431 –ofdanishefsky’sdiene Homoallylic amines 431, 591 (1-methoxy-3-trimethylsilyloxy- – prins cyclization 431 1,3-butadiene) with aldehydes 865 homoallylic chlorides 569 Index 1087

Homoallylic hydrazines 591 Hydrolysis 895 Homoallylic sterols 449 – of meso-epoxides and kinetic Homoallylstannane 478 resolution of terminal epoxides 895 Homobimetallic lanthanide catalysts 671 Hydroperoxyacetals 233 Homocoupling 987 Hydrophosphonation 272 – of alkyl Grignard reagents 987 – of aldehydes with dimethylphosphite Homolysis 272 – of Organogallium(III) compounds – of aldimines 272 370 Hydrophosphonylation 67, 91 Homopropargyl alcohol 282, 479 – of aldimines 67 Hosomi–Sakurai allylation 475–478, 489 –ofimine 91 – of aldehydes 489 Hydrophosphonylation reaction 271–272 – silicon catalyzed 475–478 – Al catalyzed 271–272 Hunig base 616 Hydrosilanes 483 Hydrazination 71 Hydrosilylation 1029 – enantioselective 71 – of methyldiundecenylailane 1029 Hydrazine acids 680 Hydrosilylaton of ketimines 172 1-Hydrazinodiene 596 Hydrostannanes 483 α-Hydrazinonitriles 593 α-Hydroxy ketone 203, 1001 Hydrazone 168, 197, 590, 680, 682, 832 3-Hydroxy-1,5-enynes 1009 – catalytic asymmetric hydrocyanatin – benzannulation 1009 682 α-Hydroxy-γ-Ketoesters 606 – cycloaddition 197 β-Hydroxy ketone 203, 1025 – Mannich-type reactions 590 β-Hydroxypropargylamines 204 Hydride reductions 1022 δ-Hydroxy-β-Ketone esters 745 Hydride transfer reaction 545 3-Hydroxy-2-arylacrylic acid ethyl ester 879 – Sn(II) and Sn(IV) Lewis acid 5-Hydroxy-3-ketoesters 801 promoted 545 5-Hydroxy-4,4-difluoro-2-alken-1-ol 243 Hydroamination 48–50, 580, 794–800, α-Hydroxy enones 944 1010 β-Hydroxy thioethers 571 – Au catalyzed 1010 γ-Hydroxyalkenes 803 – bismuth-catalyzed intermolecular – asymmetric intramolecular 580 iodocyclization 803 – Effect of aniline substitution 48 Hydroxyalkylation 248–250 – of vinyl arenes 49 – Al catalyzed 248–250 – other unsaturated substrates 50 α-Hydroxyamides 508 – Ti catalyzed 795–800 o-hydroxybenzaldehydes 602, 617 Hydroarylation 48–50, 578 – cyclocondensation 617 – Effect of aniline substitution on 48 2-Hydroxychalcones 397, 563 – of alkenes 578 – In(III)–SiO2 catalyzed cyclization – of vinyl arenes 49 397 – other unsaturated substrates 50 – intramolecular cyclization 563 Hydrobenzoin 978 α-Hydroxyesters 508 (S,S)-Hydrobenzoin 150 α-Hydroxyethylene-2-indanone 122 Hydroboration polymerization 1026 3-Hydroxyflavin 87 Hydroboration reaction 1021 Hydroxylbenzaldehyde 893 – on the polymer 1021 Hydrocyanation 75, 264–272, 680 – Al catalyzed 264–271 i – aluminum catalysts 266 6,6 -I2BINOL 750 – of aldimines 75 IMDA reactions 310 – of aromatic imines 272 Imidazolidin-2-ones 495 – of hydrazones 680 Imidazolium chloroaluminate 248 Hydrodefluorination 501 Imidazolyl chloride 356 1088 Index

Imido titanium 796 indanone oximes 568 Imidotitanium complex 796 – rearrangement 568 Imine 268, 454, 496–498, 597, 649, 733, 793, 1-indanones 599 795, 932, 990, 998, 990 Indanooxazolidin-2-one 991 – addition of phenylacetylene 932 Indeno[1,2-b]benzopyran 602 – allylation 733 Indium complex chiral 455 – reduction 794 – pathways for the formation 455 Imine allylation 215–218 Indium enolate 442 – with boron Lewis acids 215 Indole 391, 393, 409, 440, 440, 798 Imine–Lewis acid complex 158 – acylation 409 – Ag(fod)-catalyzed [1 + 2] – addition catalyzed by InCl3 393 cycloadditions 990 – addition reaction 391 – asymmetric reduction 793 –InBr3-catalyzed synthesis 440 – competitive allylation reaction 649 – polysubstituted 440 –[1+ 2] cycloaddition 597 – sulfonation 409 – hydrocyanation Al-mediated 272 Indolinones 559 – hydrogenation 793 – synthesis of pyrrole-substituted 559 – hydrocyanation to with HCN 268 Indolizidines 199, 324 –R3SiX-promoted reactions 496–498 – natural polyhydroxylated 324 – reduction 454 1,2,7,8-indolizidinetetrol 498 Imines, phenol-derived 12 Indolizine alkaloid 914 – enantioselective allylation 12 β-Indolyl alcohol 1053 Imino Diels–Alder reactions 953 1-Indolyl-1-alkylamine 94 • – catalyzed by CuClO4 MeCN 953 3-indolylarylmethanamines 908 Imino ene reaction 646 3-indolylquinones 393 – catalyzed by Yb(OTf)3 646 Intermolecular cooperative dual catalysis 686 α-imino esters 929, 999 – [(salen)Al]2O complex and – PMP-protected 929 (PyBOX)ErCl3 complex 686 Imino–aldol reactions 210 Intramolecular cooperative catalysis 709 Iminodienophiles 194 – postulated Lewis acid–Lewis acid – with B (III) catalysts 194 709 Iminoester 937 Intramolecular Friedel–Crafts acylation 599 – AgOAc-catalyzed cycloaddition of – of benzyl Meldrum’s acids 599 999 Intramolecular hydroamination 604 –[1+ 2]-type 937 – using Sc complexes 604 Iminooxazoline 170 Intramolecular Michael like process 309 Iminophosphonate 937 Inverse electron-demand 757 – allylation of 937 N-iodo succinimide 803 In(III) Lewis acids Iodoalcohol 850 – activation of hard and soft Iodocyclization 803 nucleophiles 390 α-iodolactone 335 In(III)–BINOL catalyst 456 Iodolysis 527 In(III)–BINOL complex 455 – regio- and stereoselective 527 In(III)–diselenide complex 448 Iodopyridines 176 In(III)–PYBOX complex 456 Ionic liquids 247 In(OAc)3 381 – immobilized 247 In(OTf)3−n(OAc)n 445 (R)-(−)-ipsdienol 748 In(OTf)3 379, 387, 399, 415, 421, 423, Iridium(I) complex 886 445 Iron–pybox complexes 879 In(OTf)3 –alkyne complex 405 Isocarbocycline analogs 752 In–InCl3 system 448 Isocyanophosphorane 3 (+)-INDABOX 863 Isomerization reactions 203–209 (−)-[(INDABOX)(p-cymene)RuCl]SbF6 863, – B(III) Lewis acid based 203–209 864 1-isopropenyl-2-methylbenzene 502 Index 1089

Isopropyl glyoxylate 504 – electrophilic fluorination 790 Isopropyl pybox catalyst 879 – intramolecular addition 1005 Isopropylbenzene 363 – one-pot enantioselective Isopropylmagnesium amide 144 heterodihalogenation 790 Isoquinoline alkaloid 68 Ketohydrazone 680 Isoquinolinium 269 Ketoimines 677 – cyanide additions 269 – catalytic enantioselective Strecker Isoxazolidine 145, 763, 847 reaction using Gd catalysts 677 Isoxazolidine cycloadducts 960 Ketone 53 Isoxazolidinones 145 – michael addition 53 ITM-2 122 Ketone acetalization 357 Ketone enolates 1002 j – Catalytic enantioselective protonation JandaJel-supported BINOL-AlCl 1033–1034 1002 Jorgensen’s hydration model 65 Ketones 8, 10, 193, 219, 262, 356, 358, 367, Jorgensen’s model 64 385, 381–391, 442, 444, 456, 649, 671, 691, 722, 729, 731, 732, 737, 774, 775, 935, 992, k 1004, 1023 K(I) Lewis acids 109–130 – alpha-ethynylation 367 Kelly’s bisphenol 65 – 1,2-additions 381–391 Ketene dithioacetal 297, 765 – a reaction Al catalyzed 308 –[2+ 2]cycloaddition of 297 – acetalization 444 Ketene silyl acetals 7, 210 – addition of acetylenes to, Cu catalyzed – enantioselective Michael addition 7 935 Ketenes 295, 299 – addition of allylsilane 732 –[1+ 2]cycloaddition 295 – addition reaction 390 –Me3Al promotes [1 + 2]cycloaddition – allylation 456 of 299 – allylation Ti catalyzed 737 Ketenesilyl acetals 919 – asymmetric addition of alkynylzinc Ketimines 793 731 – hydrogenation 793 – asymmetric alkylation, Ti-complex α-keto esters 976 mediated 722 – aromatic and aliphatic 976 – asymmetric vinylation 731 – asymmetric transfer hydrogenation – borane reduction of 1023 976 – catalyst 193 β-keto esters 974, 975 – catalytic asymmetric addition of alkyl – acyclic and cyclic 974 group 729 – enantioselective fluorination 975 – catalytic asymmetric 2-keto esters 973 Meerwein–Ponndorf–Verley β-keto phosphonates 924, 975 reduction 691 – addition reaction Cu catalyzed 924 – catalytic double-activation for – chlorination 975 enantioselective cyanosilylation of – deprotonation 924 775 α-Ketoacid 60 – catalytic enantioselective allyl and – reacted with benzene 60 crotylboration 10 Ketoazides 526 – chemoselective nucleophiilc attack on Ketoepoxides 284 219 – kinetic resolution 284 – cyanation 649 α-ketoesters 729 – cyanation lanthanide catalyzed 651 – catalytic enantioselective addition of – cyanosilylation La catalyzed 671 diethylzinc 729 – cyanosilylation with Gd/catalyzed β-ketoester 790, 833, 988, 1005 672 – catalytic asymmetric fluorination – deprotonation of monoethynylated 790 358 1090 Index

Ketones (contd.) Lanthanide isopropoxide 671 – enantioselective addition of Lanthanide Lewis acid 635–656, 670–710 allyltrimethoxysilane 992 – achiral 636 – enantioselective asymmetric – chiral 656–670 allylboration 8 Lanthanide metal cyanide 672 – enantioselective cyanosilylation of Lanthanide-crown ether 668 774 Lanthanides – enantioselective ethylation of 729 bis(perfluoroalkanesulfonyl)amides 655 – hydride reduction by MAD 262 Lewis acid-surfactant combined catalyst 621 –InCl3-catalyzed deoxygenation of Lewis acid 45, 52, 62, 109–130, 347–374, aromatic 442 470, 551–582, 589, 635, 825–856, 903–980, –InI3 catalyzed allylation 385 987–1011, 1019–1056 – nonracemic 1004 – bulky organoaluminum 471 – protection of 444 – immobilized to polymers 1019 –reationGaCl3 Catalyfed 356 – Lanthanide 635 Ketones α-endiynylated 367 – polymer-supported 1019–1056 Ketones, phenol-derived 12 – polystyrene-containing boron 1020 – enantioselective allylation 12 – Sc and Y 589 Ketoximes 575 – titanium 721 – cleavage 575 Lewis Acid Activation 348–361, 369–370 KF·18-crown-6 ether 994 –byInteractionswithσ Electrons kinetically enhanced metalation 127 369–370 Kinugasa reactions 962 Lewis Acid Polymeric 1020–1029 Knoevenagel condensation 432 – Boron-Containing 1020–1029 – In(III) Lewis acids catalyzed 432 Lewis acid-assisted chiral Brønsted acid (chiral Knoevenagel reaction 801 LBA) 9 – Ti catalyzed 801 –use 9 Lewis Acid-assisted chiral Brønsted acid (LBA) l 20–23 La(O–iPr)3 705 Lewis Acid-assisted chiral Lewis acid (LLA) La(O–iPr)3/linked-BINOL complex 692 12–19 La(O–iPr)3/NMe-linked-BINOL 693 – generation of 12–19 La-K-BINOL (LPB) complex 272 –use 14 (+)–lactacystin 680 Lewis acid-Lewis acid cooperative catalysis β-lactam 960 – Proposed working model of 19 – by Cu catalysis 960 –usingYLB 19 β-lactam via 641 Lewis Acid–Brønsted Base Catalyst 707–708 –synthesis 641 Lewis acid–Brønsted catalysis 645 β-lactams by 962 Lewis acid–Lewis base 162 – α-allylated 962 Lewis acid–Lewis base bifunctional catalyst β-Lacton 9 266, 267 Lactone 148 Lewis acid–Lewis base catalysis 164 β-lactone 8, 616, 743 Lewis acid–Lewis base interactions 365 – catalyzed by the chiral oxazaborolidine Lewis acid–surfactant combined catalysts 9 1036 δ-Lactone derivatives 86 Lewis acidic polymeric boronates 1020 – enantioselective 86 Lewis acidic silacycles 504 – synthesis 743 – Use 504 δ-lactone 761, 953 Lewis acidity 109 Lanthanide contraction 635, 699 – Ag(I), Au(I), and Au(III) 987–1011 Lanthanide bimetallic catalyst 670–694 – Bismuth (III) 551–582 Lanthanide complex 651 – Cu(I) and Cu(II) 903–980 – silylene-bridged 651 – Ga(III) 347–374 Lanthanide cyanide 672 – Li(I), Na(I), and K(I) 109–130 Index 1091

– Mg(II), Ca(II), and Zn(II) 135–182 MABR 329 – Polymer-supported 1052 MAD 308, 332 – Zr(IV) and Hf(IV) 825–856 Magic acid 43, 45 Lewis acids 187–236, 241, 250, 377–459, Malonate 76 469, 537, 517–547, 859–897, 1019 – enantioselective 1,4-addition 76 – ‘water-tolerant’ 527 Malonitrile 70 – Al(III) 241 – Michael reaction 70 – boron (III) 187–236 Manganese(III) acetylacetonate 892 – Classification 537 Mannich reaction 831, 992, 998 – design 250 – Asymmetric vinylogous 998 – for reaction pathway control 187 – direct 831 – from vanadium to platinum – of benzophenone imine glycine alkyl 859–897 esters with N-tosyl imines 922 – In(III) 377–459 Mannich reaction asymmetric 458 – new types of boron-based 234–235 – catalyzed by In(III)-linked–BINOL – nonchelating 203 complex 458 – photoswitchable 235 Mannich-type reaction 30, 89, 97, 154–160, – silicon 469 158, 221, 396, 555–556, 590, 608, 638, 639, – Sn(II) and Sn(IV) 517–550 640, 637–641, 747, 830, 883, 919–925, 997 Lewis acids, metal 1019 – Ag catalyzed 997 Lewis base 45 – based on Lewis acid and Lewis base Lewis base activation of Lewis acids 506 160 Lewis basic phosphine 229 – Bi(III) Lewis acids promoted Lewis basic site 57 555–556 Lewis basicity 109 – catalyzed by chiral BBA 30 Li [La(binol) (biphenol)] complex 703 3 2 – catalyzed by Yb(OTf) 638 Li(I) Lewis acids 109–130 3 – Cu catalyzed 919–925 LiClO 117 4 –inaqueousmedia 640 Limonene 550 – In(III) Lewis acids catalyzed 396 LiNTf 112, 117 2 – lanthanide catalyzed 637 Lithium amides 126 – of enol silyl ethers 638 Lithium diisopropylamide 359 – of ketene silyl acetal 89, 97 Lithium enolates 826 –ofN-(α-aminoalkyl)benzotriazoles Lithium Lewis acid 113 – Bidentate 113 catalyzed by Yb(OTf)3 639 Lithium salts 110 – of organotrifluoroborates 221 – Lewis acidity 110 – of silyl enolates 555 (S)-LLB catalyst 701 – scandium and yttrium catalysts 608 – Sc(OTf)3-catalyzed 590 (S)-LLB-type Li3[La(biphenol)3] complex 702 – N-sulfonyl imines 925 LLB–KOH catalyst 703 – three-component catalyzed by LLB–LiOTf catalyst 705, 706 Yb(OTf)3 640 – Ti catalyzed 747 Ln(O-i-Pr)3 688, 696 LnCl3 –PyBOX complexes 671 – using chiral palladium complexes • LnCl3 2LiCl 181 883 LPDE 112, 115, 119, 122 – Zn(II)-catalyzed 154–160 2,6-lutidine 293, 483 –Zr(IV)andHf(IV)Lewisacids (+)-Lycopladine A 1005 Catalyzed 830 Lyotropic liquid-crystal 1037 MAPH 324 Markovnikov hydroamination products 799 m Markovnikov products 795 M3[Ln(binol)3]-type complexes 696, 697 Markovnikov regioselectivities 407 – possible configurations 697 Markovnikov’s rule 529 – structure 696 Markovnikov-adducts 796 1092 Index

Maruoka’s chiral bis-titanium Lewis acid 15 Methyl acrylate 188 Me3SiOTf 470 O-methyl aldoximes 742 MeAl[(S,S)-salen] 291 Methyl aluminum binaphtoxide 253 Mediterranean fruit fly attractant 305 Methyl aryl sulfides 789 Meerwein–Ponndorf–Verley Reduction – oxidation 789 273–277, 691 Methyl crotonate 252 – Al mediated 273–277 Methyl ketones 3 – Ketones 691 – enantioselective cyanosilylation 3 Meerwein–Ponndorf–Verley reduction 693 Methyl rocaglate 87 – Catalytic asymmetric 693 Methyl trichloroacetate 995 Meldrum’s acid 941 Methyl trifluoropyruvate 391 Menthol 853 – addition of aromatic ring 391 (−)-menthol 315, 853 Methylaluminoxanes 327 Menthyl acetate 853 Methylaluminum Merrifield resin 1021, 1040, 1054 bis(2,6-di-tert-butyl-4-alkylphenoxide Mesityl oxide 43, 252 – derivatives) 263 Metal-centered chiral catalysts 63 Methylaluminum Metallic aluminum 302 bis(2,6-di-tert-butyl-4-alkylphenoxide), 263 Methacrolein 308, 312, 756 Methylaluminum bis(2,6-diphenylphenoxide) – A reaction Al catalyzed 308 262, 522 – Diels–Alder reaction/ring expansion Methylcyclohexane 370 312 – carbonylations 370 Methallyltributyltin 335 Methylcyclopentane 626 N-4-methoxy-3-methylphenyl aldimines 272 2-Methylcyclopentanone 358 1-methoxy-1,3-butadiene 757 2-Methylene aziridines 197 • 1-methoxy-3-(trimethylsiloxy)-1,3-butadiene – coordination of BF3 OEt2 197 661 2-Methylene-1,3-cyclohexanedione 644 2-methoxy-2-methyl-[1,3]dioxan-5-one 597 Methylene cyclopentane 970 Methoxy-2-(o-methoxyphenyl)oxazole 253 Methylene cyclopropanes 198–199, 230 –[3+ 2] cycloaddition 253 – annulations 198–199 Methoxy-2-(aryl)oxazole 253 – boron (III) Lewis acid catalyzed 230 p-Methoxyacetophenone 1038 Methylene cyclopropyl ketone 230, 526 O-Methoxycarbonyl-α-diazoacetophenone Methylenecyclopropane 523–525, 569, 596, 615 843 2-Methoxyfuran 619 – ring opening 569 2-Methoxynaphthalene 408 – ring-opening reaction 523–525 – acylation catalyzed by InCl3 408 – silyl-substituted 525 4-Methoxyphenol 249 Methyleneoxindole 618 p-Methoxyphenyl amine 932 –[5+ 2] cycloaddition 618 N-(4-Methoxyphenyl)imines 608 4-Methylenetetrahydropyrans 477 P-Methoxyphenyl 604 (+)-N-Methylephedrine 160 2-Methoxyphenyl-1,5-carboxaldehyde 215 – Zn(OTf)2 160 2-Methoxypropene 745 (1R,2S)-N-Methylephedrine-O-propionate N-Methyl-bis[(R)-1-(1-naphthyl)ethyl]amine 740 664 (1R,2S)-(−)-N-Methylephedrine 773 α-Methyl buta-1,3-diene 755 6-Methylhepta-4,5-dienylamine 800 1-Methyl-1,3-butadiene 322 N-Methylmaleimide 304 2-Methyl-1,3-butadiene 753 N-ortho-Methylphenyl maleimide 320 2-Methyl-1-tetralone 1004 2-Methylpropanoate ester 833 2-Methyl-2-phenylpropanal 356 (2-Methylpropenyl)pyrrolidine 800 Methyl 2-Methylpyrrole 798 3-(trialkylsilanyloxy)-2-diazo-3-butenoate α-Methylstyrene 970, 972 589 (6-Methyltetrahydropyran-2-yl)acetic acid Methyl 3-methyl-2-butanoate 252 564 Index 1093

Meyer–Schuster rearrangement 1006 – catalyzed by methanofullerenes 883 – Au catalyzed 1006 – catalyzed by Yb(OTf)3 642 Mg(II) ate complexes 175–181 – catalyzed by Yb(OTf)3 on silica Mg(II) complexes 136, 140, 147, 175, 876 support 643 Mg(II) Lewis acids 135 – cyclic enones with malonates 692 Mg–salen complex 865 – formation of heterocycles 555 MgI2 complex 148 – hetero 394 Michael addition 6, 72, 74, 168, 218, 287, – in the presence of TMEDA 643 288, 291, 293, 294, 360, 394, 533–534, 881 – β-keto esters and α-nitro esters – bismuth (III) Lewis acids promoted catalyzed by Yb(OTf)3 643 554–555 – Lanthanide catalyzed 687–691 – by chiral aluminum Lewis 287 – LASC-catalyzed 622 – enantioselective 74 – of ethyl acetoacetate and methyl vinyl – intramolecular 288 ketone in water 642 – Lewis acid-controlled Sn(II) and – of indanone and tetralone β-ketoesters Sn(IV) 533 611 – malonic diesters to cyclic enones 291 – of malonate 70, 81 – malononitrile and – of pyrrolidone 68 nonsubstituted/substituted – scandium catalysts 611–613 cyanoacetates 293 – Sc(OTf)3 592 – of acetyl acetone to nitroalkene 72 – N-silylenamine catalyzed by Yb(OTf)3 – of carbon nucleophiles 291 644 –ofindolestoα,β-unsaturated ketones – α-substituted malonates 692 293 – using (R,R)-LaO-iP)3/Linked-BINOL – of ketene silyl acetals to α, β-enones complex 694 6 – versatile 555 – of malonate to 2-cyclopentenone 360 – with Ca(II) catalysts 150 – of malonates to α,β-unsaturated –withβ-keto esters and cycloalkenones carbonyls 293 642 – of malonates to cyclic enones 287 Michael-type addition 391, 433 – of nitromethane or malononitrile to – In(III) Lewis acids catalyzed 433 unsaturated carbonyl compounds – silyl enol ethers 391 881 Michael-type hydroarylation 578 – of oxime derivatives 294 (R)-MNEA 664 – phosphonates to cyclic enones 291 (S)-MNEA 664 – phosphonates to cyclohexanone 291 2-MOM-pyridazinone 231 – syntheses of 1,3-bisindolyl compounds Monobenzoylated diol 978 394 Monobromoborane dimethyl sulfide complex –usingthechiralBLA 6 188 – Zn(II)-catalyzed 168 Morita–Baylis–Hillman reaction 28, 29, 68, Michael addition of diallylisopropylsilane 88, 541, 832 218 – Brønsted acid catalyzed asymmetric Michael addition reactions 286–294, 999 29 – Ag catalyzed 999 – by BINOL derivative 88 – Al(III) Lewis acids mediated – of imines with ynones catalyzed by 286–294 ZrCl4 832 Michael adducts 71 Morita–Baylis–Hillman reaction 74 Michael reaction 68, 70, 81, 150, 394, 622, – enantioselective 74 642, 555, 592–593, 611–613, 642–644, Morita–Baylis–Hillman-type reaction 494 687–694, 694, 883 871 –ofα-enones with acetals 494 – between methyl vinyl ketone and ethyl Mucohalic acids 381 cyanoacetate 871 – reaction with acidic methylene 381 – catalytic asymmetric La catalyzed – ring-opened form 381 692–694 Mukaiyama aldol pathway 143 1094 Index

Mukaiyama aldol process 761 – Sn(II) and Sn(IV) Lewis acids Mukaiyama aldol reaction 6, 24, 25, 85, 251, promoted 532–545 379, 485–487, 507, 589, 667–668, 762, 828, Mukaiyama–Michael addition 309, 939 829, 860, 861, 914, 995, 1025, 1039, – Al catalyzed 309 – Ag catalyzed 995 – of silylketene acetals and enolsilanes – aldehydes and ketones 485–487 to alkylidene malonates 939 – between aldehyde and silyl enol ether Mukaiyama–Michael reaction 120, 612, 614 1025 –ofα,β-unsaturated ketones and enol – between silylketene acetals and silyl ethers 641 pyridine N-oxide aldehydes 914 Mulaiyama-aldol reactions 668 – Bismuth (III) Lewis acids 556–557 – in aqueous media promoted by –byFeCl3 860 Pr(OTf)3 complex 668 – catalytic asymmetric 667–668 Myers–Saito cyclization 989 − – catalyzed by TADDOL 24, 25 ( )-myrtenal 493 – effect of surfactants 861 – enantioselective 85 n N,O-ligand 163 –InCl3 –AgClO4 catalyzed 379 – of benzaldehyde 1039 Na(I) Lewis acids 109–130 – of ketene thioacetal to methyl pyruvate Nafion SAC-13 40 Nalfinavir 778 catalyzed by a Cu(OTf)2 914 – of TMS enolates 507 Nanometer-Sized Bismuth 553 NaphO–Zn(II)–R 164 – proposed transition state for the anti 2 1-naphthaldehyde 992 adduct 829 Naphthalene 369 – Sc(OTf) -catalyzed 589 3 – catalytic aromatic alkylation 369 – 1-(trimethylsilyloxy)-1-cyclohexene 2-Naphthalenethiol 1053 with benzaldehyde 251 Naphthyl alcohol 840 – vinylogous 85 Naphthyl ketone 989, 1008 –withchiralBLA 6 α-(2-naphthylimino)ester 999 –Zr(IV)andHf(IV)Lewisacids Naproxen 759 catalyzed 828 Nazarov cyclization 886, 972–973 Mukaiyama-aldol reaction asymmetric 457 – Cu catalyzed 972–973 – In(III)–PYBOX catalyzed 457 Nazarov cyclization reaction 99 Mukaiyama-aldol reactions 209, 211, 378, – catalyzed by phosphoramide 99 636 Nazarov reaction 592, 616, 989, 1007 – boron Lewis acids promoted 209 – Ag catalyzed 989 – enantioselective 211 – Au catalyzed 1007 –InCl3 –SiR3Cl catalyzed 378 – catalytic, enantioselective 616 –silylenolethersinaqueousTHF 636 Nazarov-type cyclization 490 Mukaiyama-aldol reactions 212 NCN–palladium complexes 883 – enantioselectivity and NCN–pincer complexes 883 diastereoselectivity 212 (Neomenthylindenyl)zirconocene dichloride Mukaiyama-aldol type reactions 391, 1025 850 – Boron-Containing Polymeric Lewis Neryl pyrrolidine 175 Acid 1025 Ni(II) complexes 876 – employing InCl3 391 Ni(II)-perchlorate hexahydrate 881 Mukaiyama-type aldol 537 Nickelacyclopentadiene 301 Mukaiyama-type aldol reaction 997 Ninhydrin 58, 59 – 3-trimethylsilyloxy-vinyldiazoacetate – acid catalyzed condensation 59 with aldehydes 997 Niobium(V) chloride 892 – of silyl enolates with α-ketoesters Nitrile imines 141 997 – cycloadditions 141 – of trimethoxysilyl enolates 997 Nitrile oxides 140 Mukaiyama-type reactions 532–545 – cycloaddition 140 Index 1095

Nitriles 570 Nitroso aldol reaction 27,86 – reaction with epoxides 570 – regioselective synthesis 27 Nitro aldols 160 Nitroso-Diels–Alder reactions 958 Nitro Michael reaction 74 – enantioselective 958 – with novel bifunctional thiourea Nitrosobenzene 1001, 1002 catalysts 74 β-nitrostyrenes 373 Nitro-Mannich reaction 73, 707, 926–930 – reaction with trialkylgallium 373 – Cu catalyzed 926–930 Norbornadiene 302 – lanthanide catalyzed 707 –[1+ 2 + 2]cycloaddition reactions of Nitroaldol (Henry) reaction 157 302 Nitroaldol reaction 700, 701, 701, 702, Norbornene 797 698–702, 926 – hydroamination 797 – acceleration 702 Norbornene carboxylate 307 – copper-catalyzed 926 – fluorinated 307 – diastereo- and enantioselective NTf2 47 700 Nucleophilic addition 62 – effects of the ionic radii of rare earth Nucleophilic substitutions 413–421 metals 699 NUPHOS 871 – heterobimetallic catalysts 699 NUPHOS diphosphines 886, 888 –mechanism 698, 698–702 –ofα-keto esters 701 o – proposed mechanism promoted by O–H insertion 604 LLB and LLB-II (LLB-LiOH) 701 (+)-Ochromycinone 1008 – tandem inter-intramolecular catalytic Octahydroacridines 561–562 asymmetric 700 – one-pot stereoselective 561–562 tert-nitroaldols 704 2-octanone 359 – kinetic resolution of 704 1-octyne 302 Nitroalkene 72, 324, 325, 965 –[1+ 2 + 2]cycloaddition of 302 –[1+ 2]cycloaddition 324 Of α-methylstyrene 448 – enantioselective 71 –InBr3-catalyzed reaction 448 – enantioselective and diastereoselective Of 3-exomethylene β-lactams 963 77 Of [Ru(CH3CN)(triphos)](OTf)2 893 – Michael reaction 72 Of diazoacetates 17 – tandem double-intramolecular Of epoxides 454 [1 + 2]/[1 + 2] cycloadditions 325 –InBr3-orInCl3-catalyzed conversion β-Nitroamines 77 454 Nitroaminesβ-Nitroamines 71 Of ethylpyruvate 916 3-nitrobenzaldehyde 276 Of oxovanadium–biphenolate 891 N-(p-Nitrobenzoyl)hydrazone 847 Of phenanthrenes 437 p-Nitrobenzylalcohol 1032 – metal-catalyzed synthesis 437 Nitrogen heterocycles 990 Olefin activation reactions 528–532 Nitromethane 990 Olefin cross-metathesis 225 Nitrone 15, 65, 140, 302, 498, 763, 764, 847, Olefin hydrosilylation 227 958, 960, 963 6-(3,4) olefin-ene cyclization 747 – ATPH catalyzed 1,3-dipolar Olefination 491 cycloaddition 302 – of aromatic aldehydes Ni-catalyzed – coupling of propargylic alcohol with 491 963 Olefins 51, 55, 748, 782, 793, 1010 –cyanation 65 – addition of carboxylic acid 51 – cycloaddition 140, 764, 958 – addition of phenol 51 –[1+ 3] cycloaddition Hf or Zr – anti-aminohydroxylation 55 catalyzed 847 – asymmetric epoxidation 782 – 1,3-dipolar cycloaddition 15 – Au catalyzed addition 1010 – exo selective cycloaddition 960 – Carbonyl-Ene reaction 749 1096 Index

Olefins (contd.) Oxazaborolidine derivatives 1022–1026 – disubstituted 748 – Polystyrene-supported chiral – hydroamination 51 1022–1026 – hydroboration 793 Oxazaborolidinone 1025 – hydrogenation 793 – Cross-linked polymer-supported – substrates 748 1025 Olefins 51 Oxazinones 78 Oligosaccharide syntheses 654 – kinetic resolution 78 + (R,S)–(ON )Ru–salen complex 865 Oxazolidinone 305, 754 One-pot cyclocondensation 669 – cycloadditions to 754 – Aldehyde, 1,3-keto ester, 669 – diastereoselective Diels–Alder 305 One-pot Mannich reaction 398 Oxazolidinone acrylate 945 – catalyzed by InCl3 398 Oxazolidinone cinnamate 950 – diastereoselective 398 Oxazolidinone enoates 950 One-pot multicomponent synthesis 558 – β-substituted 950 One-pot synthesis 400 Oxazolidinone isothiocyanate-substituted –usingInCl3 as catalyst 400 143 Oppenauer Oxidation 273–277 α-oxazolidinonylallenylstannanes 204 – catalysts for 274 Oxazoline 754 – Al mediated 273–277 – reaction with cyclopentadiene 754 – of benzyl alcohols 276 2-oxazoline-4-carboxylate 253 Organic reaction 46–62 Oxazoline carboxylate 253 –Brønstedacidcatalyzed 46 Oxidation reaction 576–577, 855 Organic Synthesis 112–125 – by Bismuth (III) Lewis acids – catalyzed by Lewis acids 112–125 576–577 Organo-Inorganic hybrid polymer 1038 – Zn(II) catalyzed 170 Organoalkali metal reagents 125–130 – Zr catalyzed 855 Organocopper reagents 491 Oxidopyrylium betaine 87 Organogallium 728 Oxime ethers 1023 Organogallium compounds 360 Oxirane Ring Opening 123–125 – tetra- and pentacoordinated 360 – Lewis acid catalyzed 123–125 Organogallium phenoxides 359 Oxiranes 352, 400–403 Organogallium(III) compounds 370–374 – homolysis of 370–374 – Lewis acid activation of 352 Organolithium reagents 135 – ring opening 400–403 Organomagnesium amide 144, 147 2-Oxo-3-azabicycloketones 27 Organometallic bases 126–128 – diastereo- and enantioselective Organometallic reagents 128–130 synthesis 27 µ Orthoformate 501 -oxo-type chiral bis-Ti(IV) oxide 764 oseltamivir phosphate 686 4-oxoazetidine-2-carbaldehydes 552 Oxocarbenium ion 474, 476, 478 6,6-(OTf)2BINOL 830 6-Oxabicyclo[3.2.1]octane 1009 – intermolecular reaction 478 µ Oxanickellacycles 490 -oxodititanium complexes 751 Oxaspiropentanes 123 3-oxoesters 473 1,2,3-oxathiazinane-2,2-dioxide heterocycles 1-oxoindan-2-carboxylic acid 611 608 Oxomalonate 322 1,3-oxathiolanes 444, 575 2-oxonia [3,3]sigmatropic rearrangement – in(OTf)3-catalyzed synthesis 444 450 1,3-oxathiolanes, 1,3-dithiolanes 603 – in(OTf)3 allyl transfer 450 1,3-oxathiones 224 Oxonia [3,3]-sigmatropic alkyl migration 1-oxatrienes 196 429 – cycloaddition 196 2-oxonia Cope rearrangement 474, 481 Oxazaborolidine 5, 8, 192, 1023 – silicon promoted 481 – polymeric chiral 1023 Oxonium-ene type cyclization 430 Index 1097

– of homoallylic alcohols catalyzed by Phenols 368, 574, 1010 In(OTf)3 430 – acylation 574 5-oxy-2-pyrrolidiones 496 – Au catalyzed addition 1010 Oxy-Michael reaction 642, 644 – o-ethynylated 368 – catalyzed by cerium sulfate 644 (R)-2-Phenyl-2-methoxyethanol 23 – of alcohols and α,β-unsaturated (Z)-1-phenyl-1-trimethylsiloxypropene 1037 ketones 642 4-phenyl-3-buten-2-one 58 α-oxyaldehyde 734 – acid catalyzed 58 – allylation 734 D-phenyl alanine ethyl ester 228 Oxygen-to-Carbon migration 206 2-phenyl-1-butene 793 – boron (III) Lewis acids promoted 206 – hydrogenation 793 Ozonolysis 233 Phenylacetylene 355, 987, 1008 Phenyl aziridines 598 p – 1,3-dipolar cycloaddition 598 Palladium black 228 Phenyl glycidyl ether 64 Palladium catalyst 360 Phenyl ozazoline 148 Palladium complex 349, 883 Phenyl vinyl sulfone 965 Passerini-type reaction 508 Phenyl-boron 1020 Pauson–Khand reaction 803 Phenylation 163, 1047 Pd(II) cationic complexes 869 – of 4-trifluoromethylacetophenone Pd(II) complex 871, 884 1047 Pd–POZ 870 – of imines 163 Pechmann condensation 435 Phenylbis(triflyl)methane 39 –InCl catalyzed 435 3 Phenylboronic acid 1024 Pechmann reaction 436, 567 – cross-linked polystyrene-containing – synthesis of 4-substituted coumarins 1024 567 3-phenylcyclobutanone 148 Pent-4-enoic acid, hex-5-enoic acid 990 2-phenylethanol 892 – cyclization 990 N-phenylmaleimide 964 Pentacoordinate aluminum chelate complex (1R,2R)-(+)-1-phenylpropylene oxide 1053 261 Phenylsilane 505 1,4-pentadiyne 798 Pentafluorobenzaldehyde 277 Phenylsilylalkyne 851 Pentafluorophenyl bis(triflyl)methane 31 Phenylthioacetylene 968 Pentafluorophenylbis(triflyl)methane 38 phenylthiopropene 258 Pentamethylbenzene 1004 Phosphaferrocene- oxazoline 962, 966 – alkylation 1004 Phosphanyloxazoline iridium complexes 886 Pentanal 263 Phosphine–silver(I) complexes 992 cis-perhydronaphthalene 369, 370 Phosphino-oxazoline 870, 953 – catalytic aromatic alkylation 369 Phosphoramide 506 trans-perhydronaphthalene 370 Phosphoric acid catalysts 95 Perrin titration method 82 – kinetic resolution 95 Petasis reaction 221 – substrates 95 6,6 -Ph2-BINOL–Ca(II) catalyst 151 Phosphoric acids 90–99 Ph2Zn 163 – chiral cyclic 90 Ph3P·Au(I) 1010 – novel catalysts 97–99 Ph3P·AuCl/BF3·OEt2 1004 Phosphorodiamidic acid derivative 97 · Ph-BOX 970 Ph3P AuCl 1006 (S,S)-Ph-Pybox 143 [(Ph3PAu)3O]BF4 1005 Ph-pybox 612 (Ph3P)AuOTf- 1010 6,6 -Ph2BINOL 766 Phthalocyanine–copper complex 951 Phenanthrenes 59 Pictet-spengler reaction 36, 58, 497 – from benzopinacol 59 – of imines 497 Phenolic ketone 838 Pictet–Spengler reaction 96, 400 1098 Index

Pictet–Spengler reaction (contd.) Polymer-supported Yb Lewis acids – catalyzed by phosphoric acid catalysts 1054–1056 96 Polymer-Supported Zn Lewis Acids – In(OTf)3 catalyzed 400 1051–1052 Pinacol cross-coupling 448 Polymeric borane catalyst 1029 –In/InCl3 promoted 448 Polymeric boronate 1020 Pinacol rearrangement 58, 481 Polymeric Monolith Ti–TADDOLate 1046 Pinacol type rearrangement 208, 285 polymeric Ti–TADDOLate catalyst 1045 – 3-silyloxyoxetanes 285 Polymerization 1020 – boron (III) Lewis acids promoted 208 – boron-containing monomer 1020 PINAP ligand 941 – of silicon-containing monomer 1020 2-piperazinemethanol 1023 Polymetallic asymmetric catalysts 670–694 Piperidines 257 Polymetallic lanthanide complexes 680, 685 – diastereoselective synthesis of cis and – structures of ligands 680, 685 trans-3,4-disubstituted 257 Polymethylhydrosiloxane 171, 733 Piperidone 61 1,3-polyol 691 – reaction with benzene in TfOH 61 Polyolefins 1020 Piperidone enol ether 232 – rhodium-catalyzed functionalization Pivaloate 989 of 1020 Pivalonitrile 838 polyphosphoric acid 568 Platinum(II) complex 893 Polyprenoids 21 Poly(dioxaborole)s 1028 – LBA for enantioselective synthesis of Poly(ethylene glycol) 445 21 – deprotection 445 Polystyrene 1021, 1048 Poly-condensation reactions 232 – brominated cross-linked 1021 Polycyclic heteroarenes 438 – chlorosulfonylated 1048 –In(ONf)3 catalyzed 438 Polystyrene-supported Al(OTf)3 1032 Polyene 22, 530–532 Polystyrene-supported AlCl3 1029–1032 – cyclization 22 Polystyrene-supported chiral – tandem cyclization of 530–532 Bissulfonamide-Ti 1046–1047 polyethylene 1019 Polystyrene-supported chiral N-Sulfonylamino Polyethylethylene 1020 Alcohol–Ti, 1048 Polymer 1020, 1038 Polystyrene-supported perfluoroalkyl sulfonic – borylated 1020 acid 1054 – Phenyl-silyl linkage 1020 polystyrene-supported perfluoroalkyl sulfonic – three-dimensional metal-organic ytterbium 1054 1038 Polystyrene-Supported Ti–TADDOLate Polymer incarcerated method 605 1043–1046 Polymer Synthesis 578 N-(polystyrylbutyl)pyridinium triflylimide – by Bismuth (III) Lewis acids 578 852 Polymer-micelle incarcerated method 605 Polythiophenes 1027 Polymer-supported B(C6F5)2 1028–1029 – main-chain Lewis acids of Polymer-supported BINOL–Ti 1041–1043 boron-modified 1027 Polymer-supported Cu Lewis acids 1050 Potassium cyanide 772 Polymer-supported Diol–Ti complex 1040 Potassium cyanide/18-crown-6 complex 772 Polymer-supported Fe Lewis acids 1049 Potassium organotrifluoroborates 221 Polymer-supported indium(III) Lewis acid i-Pr-PYBOX ligand 266 1052 (S,S)-i-Pr-box/Zn(OTf)2 147 Polymer-supported Sc Lewis acids ortho-prenylphenols 568 1035–1039 – rearrangement 568 – in water 1035–1036 Preparation 38 – nanostructured 1036–1037 Prins cyclization 432, 803 Polymer-supported Sn Lewis acids – for the synthesis of unsaturated 1053–1054 heterocycles 432 Index 1099

– in ionic liquids 432 Protonation 530 – suppression of epimerization – Sn(II) and Sn(IV) Lewis acids catalyzed by InBr3 432 catalyzed 530 –TiCl4-mediated 802 Pseudo-C3-symmetric trisoxazoline 907 Prins cyclizations 479 (1S,2S)-pseudoephedrine 504 – silicon promoted 479 Pt(II) cationic complexes 869 Prins reaction 532–533, 562 Pt–POZ 870 – Sn(II) and Sn(IV) Lewis acids Pt–oxazolines catalyst 871 promoted 532–533 (−)-pterocarpin 994 – Synthesis of 4-Chlorotetrahydropyrans Pudovik reaction 271 562 Pybox 877 + Prins-type annulation 477 [Sc-pybox] (Cl)2 606 – using allylsilanes 477 [Sc((S,S)-t-Bu-pybox)](Cl2)SbF6, 606 Prins-type cyclization 198, 427–431, Pyran 498 615–616 2H-pyran motif 196 – and allylation 430 Pyranobenzopyrans 617 – boron(III) Lewis acids based – cis annelated 617 198 2H-pyrans 988 – In(III)catalyzed 427 Pyranyl lactols 206 – scandium catalyst for 615–616 Pyrazolidin-3-ones 966 – syn–selective 198 Pyrazolidines 504 i-PrMgCl 178 Pyrazolidinone 960 i-PrMgCl•LiCl 178 Pyrazolidinone acrylamides 145 (i-Pr)(n-Bu)2MgLi 176 2-pyrazolines 764 Proazaphosphatrane sulfide 782 Pyridazinone 231 Propargyl alcohols 167, 261 2-pyridinecar-boxaldehyde 248 Propargyl amines 497, 932, 935 Pyridines 434, 495 Propargyl ether 499 –InCl3 catalyzed synthesis of Propargyl pivaloate 1006 tetra-substituted 434 Propargyl vinyl ethers 988 Pyridylmagnesates 177 Propargyl–Claisen rearrangement 988 N-(2-pyridylsulfonyl)imines 144 – silver(I)-catalyzed 988 Pyrogallol 20 Propargylgallium 370 Cis-pyrone 324 Propargylic alcohols 729, 1004 Pyrrole 412, 554, 619, 834, 1011 – A gold(III)-catalyzed nucleophilic – addition to Electron-Deficient Olefins substitution reaction 1004 554 – from aldehydes and alkynes 729 –InBr3 catalyzed reaction of 412 Propargylic allylic alcohols 162 Pyrrolidine 152, 964, 1000, 965, 1010 Propargylic amines 988 – cycloadducts 965 Propargylic esters 1006 4-(Pyrrolidino)pyridine derivative 83 Propargylic pivaloates 989 Pyrrolizidines 324 Propargylindiums 494 – natural polyhydroxylated 324 Propargylsilanes 478 l2-propylresorcinol – cyclocondensation 599 q 2-propylresorcinol 599 Quinine 930 10-propynyl-9(10H)-acridone 201 Quinoline 1033 Prostaglandins 320 Quinolines 434 Protection 853 –InCl3 –SiO2 catalyzed synthesis 434 – Zr catalyzed 853 Quinone motif 193 Protection Deprotection 443–446, 573–576, p-Quinoneimines 200 603 p-Quinones 395 – by bismuth(III) salts 573 – addition reaction catalyzed by InBr3 – by Sc(OTf)3 603 395 1100 Index

r Reduction 545, 792–793 Radical addition 139, 334, 669 – Sn(II) and Sn(IV) Lewis acid – Catalytic asymmetric conjugate promoted 545 669 – Ti catalyzed 792–793 – intermolecular 139 Reduction of ketones 170 –toα,β-unsaturated carbonyls 334 Reduction Reactions 170–172 –toexo-methylene lactone 334 – Zn(II) catalyzed 170–172 Radical alkylation 333 Reductive aldol reaction 441 – of cyclohexenone 333 – catalyzed by InBr3 441 Radical allylation 335 Reductive cross-coupling 448 α – -iodoimide with allyltributyltin –In/InCl3 promoted 448 335 Reductive Etherification 560, 564 Radical cyclization 332, 334 – Bismuth (III) Lewis Acids mediated – alkynylacrylate 334 564 –Et2AlCl assisted 332 Reformatsky-type reaction 449 – iodoethyl propargyl ether 332 Reissert reaction 269 Radical cyclization reactions 136, 202 – of isoquinolines with l-menthyl – bromine-transfer 136 chloroformate 269 – catalytic enantioselective – of nicotine amides 269 PhSe-group-transfer 136 – with chiral aluminum Lewis acid 269 Radical deuteration 332 Reissert compounds 269 –ofα-selenyl sulfoxide 332 Reissert-type reaction 1033 Radical polymerization 1020 resorcinarenes 565 Radical Reactions 136–140, 137, 331–336, Retro-nitroaldol reaction 701 909–911 Ring opening 675, 681–686, 841–843 – Al catalyzed 336 – Catalytic enantioselective meso-epoxide – Cu catalyzed 909–911 675 – diastereo- and enantioselective 137 –ofmeso-aziridines by cyanide 683 – Mg(II)-Catalyzed 136–149 –ofmeso-Epoxides and meso-Aziridines Raney nickel reduction 607 681–686 Rare earth bimetallic asymmetric catalysis – of oxiranes is catalyzed by Zr or Hf 671 841 Rare earth metal-peroxide 688 – of Three-Membered Cyclic Rare Earth–Alkali metal heterobimetallic Compounds 841–843 complexes, 695–698, 697 – with phenyl lithium 681 – Preparation 697 Ring opening reaction 279, 282, 280, 284, (−)-Rasfonin 6, 8 523–528, 593–594, 613 (−)-rasfonin – Al mediated 279 – Mukaiyama aldol reaction promoted – by Sc(OTf)3 593 by chiral BLA 8 – β-eliminative 284 Rautenstrauch rearrangement 1007 – of fluorinated epoxides 282 – Au catalyzed 1007 – scandium catalyzed 613 Reaction 777 – substrates for 280 Rearrangement 203–209, 208, 285, 417, 481, Ring-expansion reaction 285 567–569 Ring-opening 683 – Al mediated 285 – Catalytic enantioselective meso-epoxide – B(III) Lewis acid based 203–209 with TMSCN 683 • – catalyzed by Bi(OTf)3 xH2O 567 Ring-opening azidation 280, 282 – In(III) based 417 – α,β-epoxycarboxylic acids 282 – silicon promoted 481 – of the epoxyalcohols with aluminum – thermodynamic 208 azide complex 280 Rearrangements Sn catalyzed 523–528 Ring-opening fluorination 594 Redox reactions 440 Ritter reaction 570, 578 – In(III) salts catalyzed 440 – Synthesis of Amides 578 Index 1101

(R,S)–Ru(II)–salen complex 865 – Microencapsulated 1038 – danishefsky’s diene 866 – Polymer-Micelle Incarcerated (+)-Rubiginone 1008 Sc(OTf)3 1039 Ruthenium complexes 867 – preparation 1038 Ruthenium phosphate complex 867 Scandium tris(dodecyl sulfate) 621, 1036 Ruthenium(III) chloride 893 Scandium tris(dodecylsulfonate) 1036 R3ZnMgCl 182 Scandium tris(perfluorooctanesulfonyl)methide s complex 589 Sakurai–Hosomi allylation 992 Scandium-(4 S,5 S)-4-CH2OTIPS-5-Ph-pybox, – Ag catalyzed 992 614 Sakurai–Hosomi reaction 388, 389, 394, 610 Scandium-(4 S,5 S)-4-CH2OTIPS-5-Ph-pybox – catalyzed by InCl3 –TMSCl 389 complex, 613 – catalyzed by scandium–pybox Scandium-based Lewis acid 622 complexes 610 – polymer-supported 622 Salan [N,N-bis(o-hydroxybenzyl)- Scandium-catalyzed reactions 620–625 1,2-diaminoethane] type ligand, 728 – aqueous media 620–625 (R,R)-SALEN 293 scCO2/poly(ethylene glycol) 589 (R,R)–(salen)–Cr(III) 866 Schiff base 738, 789 (salen)Co catalysts 894, 895 Schiff base catalysts 66, 676 – oligomeric 895 Schiff base Cr(III) complex 895 – polymer-supported 895 Schiff base ligands 743, 775, 777 (salen)Cr(III) complex 893 – achiral tridentate 777 (salen)Cr(III)X 894 – tripeptide-based 775 [(salen)Ti(µ-O)]2 770, 777 Schiff base–titanium complex 745 Salen ligand 770 Schiff-base titanium(IV) complex 761 Salen–Ti catalyst 778 Schwartz’s reagent 731 Salen–Zn(II) complexes 162 (S)-SEGPHOS 958 N-salicyl-β-amino alcohol 776 Selective coordination 250 Sc(BINOL)2Li 613 Selenylimidates 597 Sc(III)-pybox-i-Pr complex 615 Self-condensation 937 Sc(OTf)3 423, 426, 604, 605, 607, 612 Semicarbazones 575 – resin- or polymer-supported 605 – cleavage 575 Sc(OTf)3-pybox complex 616 Senecialdehyde 252 Sc(OTf)3/ionic liquid system 603 Sharpless catalyst 786 i Sc(OTf)3–( Pr-pybox) complex 612, 614 Sharpless epoxidation 782, 784 Sc(OTf)3 –PyBOX complex 660 Si(IV) Lewis acids 469–509 Sc[(R)-F8BNP]3 619 – synthetic use 470–473 Sc–pybox complex 606 Si–MCM-4 409 Scandium 589–629 Si–MCM-41 414 Scandium catalyst 590, 601, 605–606, 614 Sigmatropic rearrangement 121, 174, 205, –bearingtheH8-BNP ligand 614 596, 988, 1005 – immobilization of 605–606 – Au catalyzed 1005 – in organic synthesis 601 – boron tribromide mediated 205 – polymer-supported 590 – Lewis acid mediated 121 Scandium complex 619 – silver(I)-catalyzed 988 – bearing perfluorinated binaphthyl Silacycles 471 phosphate ligand 619 – strained and unstrained 471 Scandium indane–pybox complex 617 Silacyclobutanes 471 Scandium nonafluorobutanesulfonate 595 Silacyclopropanes 471 Scandium pentafluoroethanesulfonate 595 Silica-supported AlCl3 1034–1035 Scandium perfluoroalkanesulfonate 595 Silicon 472 Scandium trifluoromethanesulfonate – hexacoordinate 472 1038–1039 Silicon enolates 860 1102 Index

Silicon enolates (contd.) o-(β-silylethenyl)phenols 368 – hydrolysis 860 2-(β-silylethenyl)cyclopentanone 357 Silicon Lewis acids 506–508 Silylium salt 493 – activated by Lewis bases 506–508 Silylketene 767 1-Siloxy-1,5-diynes cyclizations 48 – cycloaddition 767 Siloxy alkyne 989, 991 (E)-silylketene acetal 739 –[1+ 2] cycloaddition 989 Silylketene acetals 911 – hydroamination 991 α-silyloxy-epoxides 204 Siloxy cyclobutene 989 – stereoselective ring expansion Siloxy cyclohexadiene 1008 204 Siloxy hexyne 989 3-silyloxyfurans 212 α-siloxycyanohydrins 396 Simmons–Smith type reaction 295 2-siloxydihydrobenzofuran 494 – of allylic alcohols 295 Silver iodide 987 Sm complex 691 Silver tosylate 987 Sm(O–iPr)3/H8–BINOL 690 Silver(I) halide 988 Sn(II) Lewis acids 517–547 Silver(I) triflate 990 Sn(IV) Lewis acids 517–547 Silver(I)·phosphine complexes 998 Sn(OTf)2 523, 525 O-Silyl-N,O-ketene acetals 25 Sn-X bond distances 518 Silyl carboxylates 413 sodium tetraarylborates 578 – reactions catalyzed by InCl3 –AgOTf Sonogashira coupling reaction 987 413 Sp–sp2 coupling reaction 447 O-silyl dienolate 745 Spiro-oxindoles 802 Silyl dienolates 366, 507 Spirocyclic pyran 222 Silyl enol ether 160, 212, 358, 608, 743, 745, Spirocyclopropane oxazolidinones 761, 921 768 – addition reaction Cu catalyzed 921 γ-stannylcarbenium ion 479 – BINOL-Ti-catalyzed aldol reaction (+)-stenine 313 743 Strained heterocycles opening reactions – diastereoselective addition 608 279–285 – transmetalation 358 – Al mediated 279–285 Silyl enolate 471, 473, 507, 998, 1001 Strained organosilicon Lewis acids – Aldol-type reaction catalyzed 473 503–505 – mukaiyama aldol reaction 485 Strained silacycles 503 – nucleophilic addition of aldehyde Strecker reaction 66, 68, 80, 83, 96, 268, 558, 507 675–681, 681, 776 Silyl ethers 413, 573–574 – N-allylaldimine with hydrogen cyanide – Cleavage and Conversion 573–574 66 – reactions catalyzed by InCl3 –AgOTf – Bismuth (III) Lewis acids 558 413 – catalyzed by guanidine 80 Silyl ketene acetal 608, 939 – catalyzed by phosphoric acid catalysts – Cu(II)-catalyzed addition reaction 96 939 – chiral switches in 681 – diastereoselective addition 608 – enantioselective 83 Silyl ketene aminals 991 – Ketoimines and Hydrazones α-silyl oxocarbenium 474 675–681 (R)-silylacetylene 1005 –ofN-benzyl substituted imines with Silylacetylene, silyl enol ether 367 TMSCN 776 – catalytic ethynylation 367 – of dihydroisoquinoline 68 Silylacetylenes 361 – of aromatic N-allylimines with HCN Silylallylgallium 353 268 Silylation of alcohols 625 – substrate for 68 – yttrium-based catalyst 625 – with chiral aluminum Lewis acids has Silyldienol ether 24 been 268 Index 1103

Strecker synthesis 74 Tamoxifen 835 – with novel bifunctional thiourea Taniaphos ligand 965 catalysts 74 Tertiary allylic alcohols 731 Strecker-type reaction 144, 268, 650, 775 – Ti catalyzed 731 – catalytic enantioselective 144 Tetraalkylated gallium compound 373 – catalyzed by Yb(Tf)3 650 α, α, α , α -Tetraaryl-1,3- –ofN-fluorenyl aldimines with TMSCN dioxolane-4,5-dimethanol derivative, 83 268 3,3,5,5-tetrabromo-1,1-biphenyl-2,2-diol – Ti catalyzed 775 310 Strecker-type reactions 832 Tetrabutylammonium – mediated by Zr or Hf catalysts 832 triphenyldifluorosilicate 399 Stubborn dienophiles 311 tetrabutylphosphonium bromide 571 Styrene 1020 Tetraethynylmethanes 364 Styreneoxide 1049 tetrafluorophenylbis(triflyl)methane 2-substituted 1,3-dithianes 789 polystyrene-bound, 39 – Oxidation 789 – Catalytic activity 39 N-sulfinyl dienophiles 958 Tetrahydrofuran derivative 990 β-sulfonamide alcohol ligands 730 Tetrahydrofuran motif 216 Sulfone 855 Tetrahydrofurans 200, 479, 525, 572 N-Sulfonyl-(S)-tryptophan 1025 – 2,3,5-trisubstituted 479 N-sulfonyl aldimines 908 – 2,5-disubstituted 525 Sulfonylation 409 – O-Acylative cleavage 572 – of activated arenes 409 – regio and stereoselective 200 Sulfonyloxirane 826 Tetrahydroindenes 219 Sulfoxidation 786–789 Tetrahydropyran 200, 222, 562 – Ti catalyzed 786–789 – synthesis 562 Sulfoxidation-kinetic resolution process 787 Tetrahydropyran derivative 990 – one-pot titanium-catalyzed tandem Tetrahydropyran-4-one 607 787 Tetrahydropyranones 474 Sulfoxide 855 – regio and stereoselective 200 Sulfur nucleophiles 54 Tetrahydropyranyl Ether 573, 1032 –combined 31 – formation, cleavage, and conversion – Michael addition 54 573 – Introduction of Electron-Withdrawing Tetrahydropyranylation 1032 Group 38–41 – of alcohols 1032 Super Brønsted acid 31, 35–36, 38–45, 40 Tetrahydropyridines 601 –achiral 35 Tetrahydrothiophene 494 –definition 35 (tetrakis(pentafluorophenyl)porphyrinato) – fluorous 40 Ru(II) complex 882 SuperBrønstedacidcatalyst 29–31 Tetrakis(pentafluorophenyl)borate ion 470 Superelectrophile 56–62 Tetrakisamido titanium complex 799 Syn aldol 139 2,2 ,4,6-Tetramethylbenzophenone 171 Syn-aldol adducts 144 N,N,N ,N -Tetramethylethylenediamine 642 Syn-diastereoselective aldol reactions 143 Tetraol 89 Synthons 850 Tetraphos–Pd complex 884 Tf2NH 47, 49, 53, 54, 55, 195 t TfN[Al(i-Bu2)]2 311 TADDOL 24, 25, 335, 723, 761, 1043 TfN[Al(Me)Cl]2 311 – Representative structures 24 TfNH2 46, 48 TADDOL–Ti reagents 803 TfOH 46, 50, 53 TADDOL–Ti(OTs)2 763 (TfOH) 160 TADDOL–TiBr2 761 The single-pass reaction column 40 TADDOL–TiCl2 754, 761, 763, 765, 768 The solution phase acidity 37 TADDOL–titanium complexes 724 The takemoto’s catalyst 72 1104 Index

(+)-Thiamphenicol 991 Ti(IV)(TADDOLato) catalyst 790 Thienyl carbonate 853 Ti(IV)-(S)-BINOL 16 Thienyl ester 853 Ti(NMe2)2(dpma) 798 i Thienyl-boron 1020 Ti(O Pr)2 –BINOLate 1041, 1043 i Thienylmagnesate 177 Ti(O Pr)2Br2 748 i N-(2-thienyl)sulfonyl aldimines 925 Ti(O Pr)2Cl2 748 i Thiiranes 453 Ti(O Pr)4 723, 729, 747, 748, 787, 801 N-thio-acyliminium ions 497 Ti-(S)-BINOL catalyst 15 Thio-Michael addition 277 Ti–Ga–salen heterobimetallic catalyst 778 – of chiral aluminum alkoxide 277 Ti–salen [N,N-bis(salicylidene) Thioacetalization 444 ethylene-diamine] type catalysts, 729 i Thioacetals 574–575 TiCl2(O Pr)2 761 – protection 574–575 TiCl4 732, 747 α-Thioallenes 1011 TiCl4-(R)-2-phenyl-2-methoxyethanol complex – cycloisomerization 1011 23 Thiocarbonyls 559–560 TiCl4 –Bu3N 740 – conversion reaction 559–560 TiCl(OTf)3 733 Thioesters 366 TiF4 738 – α-Ethenylation 366 Tin enolate 1002 Thioglycoside synthesis 415 Tin–boron exchange reaction 1027 Thiol group 575 Tischenko products 275 – protection 575 Tischenko reduction 619 Thiolacetic acid 407 –ofβ-Hydroxyketones 619 – addition reaction 407 Tishchenko reaction 703 Thiolactones 209, 453 –ofβ-Hydroxyketones 703 – from isomerization 209 Titanium µ–oxo complex 724 Thiols 414 Titanium alkoxide 723, 733 – reaction catalyzed by In(III) 414 – cleavage 733 Thiolysis 571, 572 Titanium bis(sulfonamido)imido complex – aziridines 572 800 – of epoxides 571 Titanium catalyst 728, 760 (R)-γ-Thionodecalactone 209 – development 728 (S)-γ-Thiodecalactone 209 – by transmetallation 728 Thionolactones 209, 453 – dendritic chiral 760 – isomerization 209, 453 Titanium complexe 722, 730, 787 Thiopyridines 226 – C3-Symmetric tris(β-Hydroxy amide) – oxidative addition to Pd(0) 226 chiral ligand 731 Thiourea catalyst 66–79 – metathetic ligand exchange process – atropisomeric 75 722 – bearing acidic functional group 79 – of chiral sulfonamides 730 – bearing both guanidine and thiourea – preparation 787 functional groups 79 Titanium dimethylamino complexes 795 – bearing primary or secondary amine Titanium enolate 214 79 Titanium isopropoxide diethyl tartrate 782 – bifunctional chiral 70–79 Titanium Lewis acid 721–805 – monofunctional 66–70 Titanium tetra-tert-butoxide 741 – novel bifunctional 74 Titanium tetraalkoxide 786 – use binaphthyl backbone 74 Titanocene complexes 800 Thioureas 581 Titanocene derivatives 754 – catalytic guanylation 581 Titanocene enolates 826 Ti Lewis acids 1040–1048 TMEDA 128 – polymer-supported 1040–1048 O-TMS cyanohydrins 605 Ti(IV) complexes 166 TMSCN 266 Ti(IV) Lewis acids 232 TMSOTf 607 Index 1105

α-Tocopherol 499 Trifluoroacetaldehyde ethyl hemiacetal p-Tol-BINAP·AgF 995 387 (R)-p-Tol-BINAP 992 – in-mediated allylation 387 (R)-Tol-BINAP·AgOTf 999 Trifluoroacetic acid 194 (R)-Tol-BINAP·AgOTf to 1001 Trifluoroacetic anhydride 246 (R)-Tol-BINAP/CuPF6 complex 905 (1R,2R)-2-Trifluoroacetylamino-1-phenyl-1- (S)-Tol-BINAP·AgNO3 992 propanol 476 Toluene 362 α-(Trifluoromethyl)-α,β-unsaturated amides, – electrophilic aromatic substitution 220 362 1,4-trifluoromethyl-ation ketones 286 N-Tosyl enamine–alkyne carbocyclization β-Trifluoromethylated allylic alcohols 386 989 Trifluoromethylation 286 N-Tosyl-α-imino ester 924 N-Triflyl phosphoramide 99 N-Tosyl aziridines 401 Triisopropylsilyl triflate 597 N-Tosyl imine 922, 953, 956 2-(Triisopropylsilyloxy)acrolein 597 N-Tosylated γ-amino olefin 1010 Trimethoxysilyl enolates 995 Transesterification 852 4,7,7-trimethyl-3,4,5,6,7,8-hexahydroben- – Zr or Hf catalyzed 852 zopyran-2(H),5-diones, 881 Transfer hydrogenation 976 Trimethyl orthoformate 602 – Cu catalyzed 976 Trimethylalkynylsilanes 417 Transition-metal atoms 860 Trimethylallylsilanes 417, 419 –usedforLewisacid 860 Trimethylenemethane 381 Transition-metal Lewis acids 859–897 – cycloaddition Pd-catalyzed 381 Transmetallating reagent 384 Trimethylhydroquinone 499 Transmetallation 384, 387, 414, 553 Trimethylorthoformate 1038 – bismuth (III) Lewis acids promoted 2-trimethylsiloxyfuran 498 553 1-trimethylsilyl nitropropanate 608 Transthioacetalization 444 Trimethylsilyl azide 401 Tri(i-propoxy)titanium chloride 742 Trimethylsilyl bis(fluorosulfonyl)amide 473 Tri-n-octylammnium salts 44 Trimethylsilyl – vN–H frequencies 44 bis(trifluoromethanesulfonyl)amide 470 Trialkylaluminum 253, 333 Trimethylsilyl cyanide 3, 878 Trialkylaluminum compounds 725 Trimethylsilyl enol ether 589 Trialkylgallium 359 Trimethylsilyl enolates 473, 1002, 1003 N-Trialkylsilyl imines 210 – asymmetric protonation 1002 Trialkyltin enolate 994 – enantioselective protonation of 1003 Triaryloxy borate ester 234 Trimethylsilyl iodide 473 3,3-bis-triarylsilylated BINOLs 322 Trimethylsilyl ketene acetal 213 (1H)-1,2,3-triazole 1035 O-Trimethylsilyl monothioacetals 441 Triazole antifungals 674 – reduction 441 Tributyltin triflate 8 Trimethylsilyl nitronates 929 Trichloroacetylisocyanate 483 Trimethylsilyl nitronates 929 Trichlorosilyl aldolate 507 Trimethylsilyl pentafluorophenyl Tricyclic nitrosoacetal 325 bis(trifluoromethanesulfonyl)methylide, Tricyclic silyl aldolate 487 499 1,7,9-trienes 310 Trimethylsilyl trifluoromethanesulfonate Triethylborane 372 469 Triethynylvinylmethane 364 Trimethylsilylated nitrogen 469 Triflate 193 Trimethylsilylcyanide 649, 768–770 Triflic acid 192 Trimethylsilylmethylenecyclopropyl imines Triflimide 192, 193 199 Trifluoro ethyl hemiacetal 390 – endo cyclization 199 Trifluoro ethylpyruvate 906, 916 2-trimethylsilyloxyfuran 612, 745 1106 Index

Triorganosilylium ions 485 (E)-vinylsilane 851 3,5,8-trioxabicyclo[5,1,0]octane derivatives Vitamin D3 analogs 752 778 – aminolysis 778 w 1,3,5-trioxanes 453 (−)-wilforonide 333 Triphenoxy borate ester 234 Wilkinson’s catalyst 224 Triphenylphosphine 863 Triphenylphosphine oxide 3, 6 x Tris(pentafluorophenyl)borane 210, 214 Xabox 877 Tris(pentafluorophenyl)borane Lewis acid Xabox-i-Pr-Mn(II) 861 209 Xabox-Bn-Mn(II) 861 Tris(perfluoroalkanesulfonyl)methide Xabox–Bn–Mg(II) complexes 877 655 Tris(perfluorobutanesulfonyl)methide 655 y Tris-pentafluorophenyl boron Lewis acid Yb(OTf)3 607 195 Yb(OTf)3 or Sc(OTf)3 380 Tris(2-pyridyl)-phosphine complex 885 Yb(OTf)3/Ph–PyBOX complex 667 Tris(trimethylsilyl)silyl Yb[(R)-BNP]3 661 bis(trifluorosulfonyl)amide 487 Yb[(R)-H8-BNP]3 complex 661 Tris(trimethylsilyl)silyl enol ethers 297 YbCl3/tBu–PyBOX complex 682 Trityl ethers 574 YbCl3/Ph–PyBOX complex 682 – cleavage 574 YCl3 626 Tryptamine homologs 799 YLB (Li3[Y(binol)3]) catalyst 708 (−)-(S)-tulipalin B 542 Ytterbium triflate 636 Yttrium 589–629 u Yttrium isopropoxide 628 Ugi–Strecker reactions 600 Yttrium-based Lewis acid catalyst 625 α,β-unsaturated 597 Yttrium-catalyzed C–O bond cleavage 626 v V(O)(OTf)2 891 z Iso-valeraldehyde 266 Zampanolide 430 Vanadium–carboxylates 892 Zimmerman–Traxler transition state model VAPOL 319 8 (S)-VAPOL 830 Zinc acetylides 497 VAPOL catalyst 228 Zirconium alkoxide catalysts 834 VAPOL-aluminum catalyst 319 Zirconium complexes for Sharpless VANOL 318 epoxidation 855 Vinyl arenes 49 Zirconium enolates 825–826 – intermolecular hydroamination and Zirconium-catalyzed asymmetric hydroarylation 49 carboalumination of alkenes 848 – of vinyl arenes 49 Zirconocene 219 Vinyl sulfones 965 Zirconocene imide 842 Vinylarenes 447 Zirconocene–imide complex 841 – dimerization 447 Zn(II) amide 168 Vinylation 731 Zn(II) Ate Complexes 175–182 – asymmetric catalytic 731 Zn(II) catalyst 156, 158, 162 Vinylation Aromatic 360 – dinuclear 158, 162 Vinylcyclohexene 851 – dinuclear chiral 156 Vinylcyclopropane 218, 478 Zn(II) complex 152, 169, 876 Vinylgallium dichloride 360 – bipyramidal five-coordinated 152 Vinylmagnesium halide 360 – dinuclear 169 Vinylpropanes 525 Zn(OH)F 168 – donor–acceptor 525 Zn(OTf)2 152, 166, 173 Index 1107

Zn–InBr3 system 448 Zr-BINOL complex 830, 834, 838, 845 Zn–Ni transmetalation 491 ZrCl4(thf)2 catalyzed 852 • ZnF(OTf) 160 ZrOCl2 8H2O 852 Zr(IV) Lewis Acids 825 Zu(II) Lewis acids 135 Zr-BINOL catalyst 828 Zwitterionic species 222