4-Acetonylindoles 110, 112 3-Acetyl-2-Alkynylpyridines 127, 128 Acetylenic Aldehydes with Indoles 94 Acetylenic Imido Complex 36

795

Index a Ag-catalyzed coupling reactions/C–H 4-acetonylindoles 110, 112 functionalization 331 3-acetyl-2-alkynylpyridines 127, 128 Ag-catalyzed C1-phosphonylation 398 acetylenic aldehydes with indoles 94 Ag-catalyzed cross-dimerization 53 acetylenic imido complex 363 Ag-catalyzed decarboxylative A3 coupling 10–11, 332–335, 645, fluorination 372 663–665, 711, 713, 761–765, 767 Ag-catalyzed 7-endo-dig Conia-ene acrolein formation 728 reaction 89 acrylamides 236, 245, 248, 251, 253, Ag-catalyzed isocyanide-based 309, 776 three-component coupling acryl sulfonamides 347 reaction 73 active methylene 127, 129, 225, 289, Ag-catalyzed oxa-Diels-Alder Reaction 363–365 67 acylarylation 234, 352, 353 Ag-cinchona alkaloid derivatives 42 acylated heteroarene N-oxides 342 Ag-complexed trans-cycloheptene 63 2-acylated pyridine-N-oxides 192 Ag-DTBM-Segphos 37 3-acylcoumarins 235, 353, 354 Ag-Feringa phosphoramidite 39 acylfluorination of styrenes 226, 227, Ag-ferrocenyl N,P-ligands 40 291 Ag-ferrocenyloxazoline 40 6-acyl phenanthridines 353 AgF-mediated coupling of styrenes aerobic alcohol oxidation 735–737 202 Ag(I)/Ag(II)-metal-organic frameworks AgF-mediated di-and 58 trifluoromethylation of styrenes Ag-BINAP 37, 70 224 Ag-catalysed and P-centered Ag-hydrocinchonine 42 radical-mediated tandem Ag-hydrotris(pyrazolyl)borate 76 reactions 347 Ag-iminophosphine-catalyzed Ag catalysis 340, 382, 622, 658, 728 aza-Diels-Alder reactions 71 Ag-catalyzed asymmetric Ag-NHC-catalyzed azide-alkyne oxa-Diels-Alder reaction 68 cycloaddition 55 Ag-catalyzed azide-alkyne AgNO3-catalyzed carbon cycloadditions 54 phosphorylation of Ag-catalyzed Conia-Ene reaction 87 arylacrylamide 346

Ag NP-catalyzed dehydrogenative catalytic hydrosilylation 647 Diels-Alder reaction 66 nucleophilic aldehyde addition 645 Ag NP-promoted photocatalytic tradition-metal-catalyzed Diels-Alder reaction 67 hydrogenation and transfer Ag-PHOX 39 hydrogenation 647 Ag-promoted azide-alkyne transfer hydrogenation 651–652 cycloaddition 56 aldehydes 43, 47, 53, 67, 68, 77, 94, Ag-promoted double cyclization of 113, 126, 149, 188, 194, 210, 216, α-iminoarylesters 50 238, 283, 334, 339, 398, 505, 508, Ag-promoted sequential 1,3-acyloxy 534, 535, 540, 541, 557, 574, migration 64 579–581, 587, 602–606, 616, 617, Ag-QUINAP 37 623, 626, 630, 633, 645–648,

AgSbF6-catalyzed C4-sulfenylation 650–655, 711, 753, 758, 770–772, 202 781 Ag-sulﬁnylimine 42 Aldol reactions Ag-Taniaphos 41 aldehydes and alkenyl trihaloacetates Ag-TF-BiphamPhos 38 604 Ag-ThioClickFerrophos 41 aldehydes and α-sulfanyl lactones

Ag2WO4/Ph3PorAg2CO3/PPh3 system 606 418 alkenyl trichloroacetates 601 Ag-Xing-Phos 46 chiral β-hydroxy carbonyl compounds Ag-XPhos complexes 71 601 akuammiline alkaloids 682 domino and tandem reactions alcohol-alcohol coupling 748–750 579–583 alcohol-amine coupling 742–748 α-ketoesters 603 alcohol dehydrogenation 734, lower diastereo-and 737–739, 743 enantioselectivities 603 alcohol oxidation nitroso-aldol reactions 606 aerobic alcohol oxidation 735–737 silyl enolates 605 alcohol-amine coupling 742–748 aliphatic carboxylic acids 19, 20, 22, alcohol dehydrogenation 737–739 23, 188, 197, 200, 204, 215, 216, benzylic and aliphatic alcohols 733 218, 226, 228, 235, 258, 289, 294, β-hydride elimination 733 322, 340–342, 352, 372, 373, 376, enthalpy of reaction 734 377, 386, 387, 395, 396, 709, 710 mechanism 733 aliphatic C–H chlorination 217 pathways and side reactions 735 aliphatic C–H trifluoromethylthiolation Sanderson’s classification of transition 203, 322 metal oxides 734 aliphatics 739 silver alloys 739–742 alkanolamines 410 aldehyde-alkyne-amine reaction 10, alkene epoxidation 727 332 ethylene oxide (EO) 724–726 aldehyde, catalytic oxidation and propylene oxide (PO) 727–729 reduction styrene epoxidation 729–733 alcohol, aldehyde and derivatives alkenes 122 652–657 hydroalkoxylation 154 catalytic hydrogenation 649–651 hydrocarboxylation 158 Index 797 alkenoic acids 154, 158, 159 alkyne-tethered benzoxazoles 141 2-alkenylanilines 387 alkyne-tethered β-ketoesters 89 alkenyl metal intermediate 417 alkyne-tethered indoles 97, 98, 682, alkoxyallene-based dihydrofurans 150 683 alkoxymethylidene cyclopropane 59, alkyne-tethered nitroolefins 89 60 alkyne-tethered pyridines 141 2-alkoxypyridine 113 alkynoates 122, 156, 245, 253, 319, 1,2-alkylarylation of styrenes 227, 228 320, 351, 352, 354 3-alkyl-4-aryldihydroquinolin-2(1H)- alkynophilicity/carbophilic nature of ones 235 silver 4–6 2-alkyl benzaldehyde 64 2-alkynylacetophenones 127, 128 alkylboronates 220, 221 3-alkynylacrylaldehydes 164, 586, 587, alkyl C–H bonds 214, 380 680, 681 alkylethynyl-benzofuran-3- 2-alkynylaniline derivatives 111, 112 carbaldehydes 126 2-alkynylaryl aldehydes 123, 126, 162 alkylethynyl-benzothiophene-2- 2-alkynylaryl aldimines 123, 124 carbaldehydes 126 3-(2-alkynyl)aryl-β-ketoesters 87 alkyl Grignard reagents, homo-coupling 2-alkynylaryl glycine imines 124, 125 of 14 alkynylations 675 alkyl halides 7, 15, 201 Ag/Pd-catalyzed ring-opening alkylidene cyclic carbonate 408, 417, reaction 616 418, 666, 667 alkyne coupling to carbon dioxide alkylidene-γ-butyrolactams 102 765–766 alkylidene malonates 37, 39, 595 alkyne cross-coupling 767–768 3-alkylideneoxindoles 366, 450, 454 allenyl boronic acid pinacol ester alkyl isocyanides 365 613–615 alkyne cross-coupling 767–768 chiral propargylamines 610 3-alkyne-1,2-diols 145 A3 coupling 761–765 alkyne-functionalized azomethines 144 1,3-diynes 612 alkynes N-aryl aromatic aldimines 611 5-and 6-endo-dig cyclizations N-sulfonylketimines 613 107–115 vinylic and aliphatic aldimines 612 5-and 6-exo-dig cyclizations alkynylaziridines 96, 97 102–107 2-alkynylbenzaldehyde 126, 127, 139, aromatic N-heterocyclic compounds 140, 161, 588, 679, 711 141–143 2-alkynylbenzaldoxime 62, 129, 130, hydrazones 134–141 132, 133, 259 hydroalkoxylation 144–155 2-alkynyl benzensulfonamides 113, hydrocarboxylation 155–159 115 imines as nucleophiles 123–129 2-alkynylbenzoic acids 155, 156 larger ring cyclizations 116 2-alkynylbenzyl azides 143, 144 oximes 129–134 alkynyl β-ketoesters 88 as partners 159–168 1-alkynylcyclobutanols 259 reduction 754–755 2-alkynyl cyclohexadienimines 62 alkyne-tethered benzimidazoles 113, alkynyl imidates 115 115 2-alkynylindoles 104, 106 798 Index

2-alkynyl-3-(silyl enol ether)quinoline α-iminoallene 121 derivatives 93 α-iminoarylesters 50 allenamide 105 α-iminonitriles 41 2,3-allenamides 363 α-indolylacrylates 370, 371 allenes 22, 522, 619 α-keto acids 192, 197, 200, 235, 236, 5-and 6-endo-trig cyclizations 240, 344 118–122 α-oxocarboxylates 237, 353, 354 exo-trig cyclizations 116–118 α-oxocarboxylic acid 192–194, 197, hydroalkoxylation 149 226, 234, 291, 342, 343, 352, 353 hydrocarboxylation 157 α-sulfinylated acrylate 44 as partners 168–169 α-thio, β-keto and α-fuoro acids 219 allenic hydroxylamines 118 α-trifluoromethylated isocyanides 53 allenylamine 427–428 aluminum oxides 730 allenyl carbamates 117 amidoallenes 121 allenylcarbinols 149 amination reaction 102, 105, 108, 117, 1-allenyl isochromenes 160 623, 624, 747 allenyne-1,6-diols 145, 146 amino acid-derived iminophosphine 1,6-allenynes 95 ligands 70 1-(2-allylamino)phenyl-4-hydroxy-but- 2-aminobenzo-tethered alkynes 105 2-yn-1-ones 105 2-aminoethanol 411 allylation 4, 7, 198, 199, 201, 340, 341, aminofluorination 228 435, 533, 534, 593, 594, 616–622 of allenes 230 allylic silanes 504, 505, 513, 518, 520, 2-amino-H-pyrazolo[5,1-α] 522, 524 isoquinolines 135 allylic sulfides 504, 522–525 2-amino-6-propargylamine azines 142 α-(acyloxy)acetates 691 2-aminopyridines 122, 283 α,α-difluoroaryloxyacetic acids 220, aminosulfonylation of alkynes 231 222 α-naphthols 240 α-allenic alcohols 149–151, 621, 677, α-naphthylamines 167 678 1,4-and 1,5-cyano group migration α-allenols 149, 620, 633 255 α-aminophosphonates 37, 398 anilines 196, 197, 238, 310, 311, 458, α-aryldiazoketones 169, 170 632, 744, 746, 776, 781 α-aryl 2-isocyanoacetate 49 anionic intermediate 417 α,β,γ,δ-unsaturated carbonyl arenes 185, 186, 191, 192, 194, 207, compounds 513 208, 210, 211, 220, 221, 227, 254, α,β-unsaturated carbonyl compound 257, 273, 298, 299, 303–305, 307, 422 310, 311, 313, 320, 337, 338, 342, α,β-unsaturated enones 60 371, 374, 375, 388, 549, 707, 775 α,β-unsaturated ketones 49, 64 aromatic acids 185, 195, 198, 206, 216,

α-CF3 ketones 225 218 α-CF3-substituted ketones 223 aromatic carboxylic acids 10 α-diazoacetamides 687 aromatic C–H bonds 382 α-diazomethylphosphonates 675 aromatic compounds 375, 387 α-fluoroketones 283, 284, 296 aromatic N-heterocyclic compounds α-H abstraction 727 141 Index 799 aromatic triazenes 191, 192, 196, 306, azides 17, 53–59, 215, 275, 465, 470, 307, 367, 368 664, 688 6-aroylated phenanthridines 353 azidoarylation 248, 249 arylacrylamides 346 aziridination 75 aryl-and heteroarylsilanes 305 intermolecular aziridination arylation and alkylation reactions 474–477 370–371 intramolecular aziridination aryl benzoates 255 471–474 arylboronic acid 191, 195, 196, 343, mechanism 477–483 357, 359, 392, 413 aziridines diazo compounds and imines arylboronic esters 413 74 2-aryl carboxylic acids 355 1-(aziridin-2-yl)propargylic alcohol aryldiazonium salts 196, 226, 288, 109 310–312, 673 azo coupling 775–776 aryl-group substituted terminal alkyne azomethine imine 63 411 azomethine ylide cycloadditions arylidene imines 34, 36, 44 Ag-BINAP 37 aryl iodides 301, 302, 304, 712 Ag-cinchona alkaloid derivatives 42 aryl isocyanides 53, 364 Ag-DTBM-Segphos 37 arylisonitriles 347, 348 Ag-Feringa phosphoramidite 39 aryl ketones 95, 342, 581, 585 Ag-ferrocenyl N,P-ligands 40 aryl migration 249–255, 260, 285, 319, Ag-ferrocenyloxazoline 40 701, 702 Ag-hydrocinchonine 42 1,4-aryl migration 251–254, 319 Ag-PHOX 39 arylnaphthalene lactones 411–413 Ag-QUINAP 37 aryl-N-oxides 343 Ag-sulfinylimine 42 arylphosphine oxides 350, 351 Ag-Taniaphos 41 arylpropiolic acids 212, 232, 248, 302, Ag-TF-BiphamPhos 38 303, 357, 391 aryl stannanes 279, 280, 392 Ag-ThioClickFerrophos 41 aryltrifluoromethylthiolation 242, 317 Ag-Xing-Phos 46 arylvinyl sulfides 393, 394 azalactones 46 Aspulvinone E 432, 434, 435 boron-containing alkene 43 α-sulfinylated acrylate 44 cascade Heck and Ag2O-promoted asymmetric counterion-directed 35 catalysis (ACDC) approach cascade protocol 44 674 diastereoselectivity 35 Aurones 145, 760 dipolar cycloaddition 34 aza-Diels-Alder reaction 67–72, 592 fluorinated imines 46 3-aza-1,5-enynes 118, 119 lactate 44 8-azaergoline 192, 193 nitroalkenes 45 azalactones 46 Oppolzer’s sultam 44 azetidine 59, 60, 77, 78 silver-promoted 34 azide-alkyne click reaction spiropyrrolidines 35, 36 57, 58 sulfinyl chiral auxiliary-based azide-alkyne cycloaddition (AAC) diastereoselective cycloadditions reaction 55, 56, 58, 688 45 800 Index

azomethine ylide cycloadditions β-aminoenones 364 (contd.) β-CF3-and β-CHF2-substituted ketones tetra-substituted pyrrolidines 36 224 trifluorormethylated pyrrolidines 43 β-enamino esters 349 azopyrazoles 452, 457 β-enaminones 52, 92 β-fluorinated γ-butyrolactones 295 β-ketopropargylamines 88 b β-keto radicals 255–257, 339 bauhinoxepin J 189 β-phosphonylated α-aryl-ketones 250 Baylis-Hillman acetates 371 β-fluorinated γ-butyrolactones 295 benzaldehyde 162, 366, 522, 564, 601, β-hydride elimination 737 617, 729, 730, 734, 735, 738, 741, biaryls 15, 356–362 746, 767, 774, 781 bicyclic guanidines 104 3-benzazepines 126, 127 bicyclic pyrrolidine 36 benzenes 16, 339 bicyclo[3.2.1]alkenes 88 benzo-7-azabicyclo[4.2.2]dec-7-en-4- bifunctional silver complex catalyzed ones 259 carboxylation 411 benzo[b]phosphole oxides 246 BINOL-derived Ag-phosphate 71, 72 benzo[b]phospholes 350 biologically active trifluoroarenes and benzo[f]imidazo[1,2-d][1,4]oxazepine perfluoroalkyl arenes 299 116 biologically important 3-acylcoumarins benzofulvenes 99 353 benzofurans 165, 194, 763, 764 bis-carbenoind 72 benzofuropyridines 126 bis-1,3-diynes 310 benzoic acid derivative 414 3,3′-bisindolylarylmethanes 113 benzoic acids 54, 184, 185, 354, 384, Boc-protected imidazolidinone 51 414, 741, 746, 771, 774, 775 boron-containing alkene 43 benzoquinones 190 boron-containing pyrrolidine 43 benzoselenazoles 141 boronic acids 205, 279, 280, 283, 359, benzothiazoles 141, 189, 256, 342, 389 361 benzothienopyridines 126 borrowing hydrogen mechanism (BHM) benzothiophenes 193, 194 742 benzoxazine-2-one derivatives 426, borylation reactions 667 428 3-borylpyrrolidine 43 benzoxazine/oxazine-fused bromsimones 66 isoquinolines and naphthyridines Brønsted acid catalysis 85, 104 128 8-(but-3-ynyl)-xanthines 113, 115 benzoxazin-2-one 428 benzoxazoles 141, 188, 189, 342, 383 benzylic C–H fluorination 220, 221, c 297, 374 Cannizzaro reaction 738 β-alkynyl ketones 126, 680, 682 carbamates 20, 117, 209, 212, 213, 250, β-alkynylpropanamides 102, 103 293, 379, 419, 421, 470, 474, 502, β-allenic primary amides 121 700, 702, 706 β-allenols 151 carbanions 183, 435, 673 β-amino-α-diazoacetates 367 carbene insertion 365, 439, 449–458, β-amino-α-diazoesters 367 668, 706–707 Index 801

carboﬂuorination 225, 226, 289–291 CO2-mediated transformation of carbon-carbon bonds propargyl alcohols 422–424 arylation and alkylation reactions enolate-sequential cyclization 370–371 431–435 biaryls 356–362 synthesis of cyclic carbonate C–H carboxylation 368–370 417–420 A3 coupling 332–335 three-component reaction of diazo-compound involved reactions propargyl alcohols, carbon 364–367 dioxide, and nucleophiles Glaser coupling 332 421–422 isocyanide involved reactions transformation of amine derivatives 362–364 424 oxidative coupling/cyclization unsaturated amine derivatives reactions 344–356 424–426 oxidative cross-coupling 340–344 unsaturated amines 428–430

oxidative-induced C–H cascade Heck and Ag2O-promoted functionalization 335–340 azomethine ylide cycloadditions perﬂuoroalkylated compounds 35 367–368 cascade radical cyclizations carbon dioxide mediated formation of C–C bonds 233–241 Meyer-Schuster type formation of C–N/P bonds 244–249 rearrangement 423 formation of C–O/S/Se bonds carbon nanoﬁbers (CNFs) 730 241–244 2-carbonyl catalytic asymmetric synthesis of cyclic H-pyrazolo[5,1-a]isoquinolines carbonate 420 135 C–B bond formation 397 carbonyl ylides 669 C–Br bond formation 377 carborane counter anion 69 C3-C3′ bis-indolin-2-ones 359 carboxylate intermediate 417 C–C bond activation 296–297 carboxylation reactions C–C bond formation-sequential aryl boronic esters 413–414 cyclization 431 cascade carboxylation and cyclization C–C coupling 187, 197, 301, 742, 748, 416–435 749 terminal alkynes 408–413 C–Cl bond formation 374–377 terminal epoxides 414–416 (-)-cephalotaxine 108, 110, 592, 684 carboxylic acids 9–10, 22, 23, 130, 185, cetyl alcohol 732 187, 204, 208, 376 C–F bond formation 8, 371–377 cascade carboxylation and cyclization chalcones 64–66, 200, 343, 344, 555 allenylamine 427–428 C–Halogen bonds benzoxazine-2-one derivatives C–Br bond formation 377 426–427 C–Cl bond formation 374–377 carbanions 435 C–F bond formation 371–374 catalytic asymmetric synthesis of C–H bond activation 297–298 cyclic carbonate 420 C–H bond amidation C–C bond formation-sequential intermolecular C–H bond amidations cyclization 431 494–498 802 Index

C–H bond amidation (contd.) 1-chloroalkynes 375 intramolecular C–H bond amidations chlorobenzene-phenylacetylene 484–494 coupling 767 mechanistic aspects 498–501 [1-chloromethyl-4-ﬂuoro-1,4-diazonia- C–H carboxylation 369, 370 bicyclo[2.2.2]octane chemoselective cyclopropanation bis(tetraﬂuoroborate),

13–14 F-TEDA-BF4] reagent 372 C–H functionalization/C–O cyclization chlorosilanes 397, 398, 778 reactions 355 C–H oxidation 687, 772–776 C–H functionalization of quinones C–H triﬂuoromethylation 192, 306, 359 337, 338 C–H functionalization via carbene cinchona alkaloid-derived squaramide transfer 445, 447–450 49, 569, 590 C–H insertion cinchona-derived phosphine ligand alkene or aromatic C(sp2)–H bonds 47 450 cinchona-derived primary amine 89, C–H functionalization via carbene 575 transfer 450–452 cinnamic acids 199, 200, 212, 340, 344 C–H functionalization via transition cis-disubstituted metal-catalyzed transfer 3,6-dihydro-1,2-oxazine 443–447 derivatives 61, 626 of ester 458–461 C–N bond formation N–H bonds 452–458 Ag catalysis 382 O–H bonds 458, 463 aliphatic carboxylic acids 386 Si–H functionalization 461 alkyl C–H bonds 380 chiral ligand (S)-TF-BiphamPhos 61 amination reaction 384 chiral N-Boc glycinates 119 aromatic C–H bonds 382 chiral N-phosphorylimine 50, 51 1,2-dihydro-2,2,4-trimethylquinoline chiral pyrrolidines 41, 556, 562, 566 derivatives 385 chiral silver phosphates disilver core 379 alkynylation 675 ethynyl carbinols 386 asymmetric hetero-Diels-Alder formamides 384 reaction 685–686 homoallylic carbamates 379 cycloisomerization 678–683 inter-molecular Ag-catalyzed α-diazoacetamides 687 amination 381 enantioselective semipinacol ligand-controlled and site-selective rearrangement 683–685 silver-promoted C–H amination hydrogen-bonding interactions 675 383 intramolecular annulation 677–678 nitration of oleﬁns 385 Lewis acid activations 674 (-)-N-methylwelwitindolinone C Mannich reaction 675–677 isothiocyanate 379 meso-aziridinium and episulfonium organic azides 386 cations 686 parent amines 384 Chloramine-T 75, 76 primary Csp3–H bonds 381 chlorinated arenes 374 silver-catalyzed intermolecular chlorinated 3-pyrrolines 120 amination 379 Index 803

silver(I)-catalyzed oxidative [4+2] cycloaddition 63–73, 77, 78, cyclization 378 164, 680, 682 Tp *,BrAg 380 Diels–Alder reaction 63 C–O bond formation 144–173, 392, hexadehydro Diels–Alder reactions 518 72–73 cocatalysts 331 oxa-and aza-Diels–Alder reactions coinage metals 435, 447, 533, 691, 741 67–72

CO2-mediated transformation of cycloalkanols 255–258 propargyl alcohols 422 cyclobutanol 256, 296 commonly used silver(I) catalysts 272 1,3-cyclohexadiene 14 concomitant protodecarboxylation cyclohexadienones 680 207 cycloisomerization 678 Conia-ene reaction 86–89, 579 alkynes as partners 159–169 conjugated ynones 432 2-alkynylbenzyl azide system 143 copper acetylide 408 allenes as partners 168 copper-mediated perfluoroalkylations aromatic N-heterocyclic compounds 301–309 141–143 coumarin-3-acids 204, 205 enynes 90–94 coumarins 147, 193, 210, 215, 245, 318 hydrazones 134–141 C–P bond formation 387–392 imines as nucleophiles 123–129 cross-coupling of arenes with alcohols 1,n-allenynes 94–95 208 1,n-diyne Compounds 95–96 C–S bond formation 392–397 oximes 129–134 Csp2-H bond functionalization 338 propargyl compounds 96–98 Csp3-H trifluoromethylthiolation 393 cyclopenta[b]chromenes 240 1,4-and 1,5-cyano group migration cyclopenta[b]indoles 104 255 cyclopentanols 256, 258, 297, 321 4-cyanopyridine 188 cyclopentenone 44, 424 2-cyanopyrrolidinines 41 cyclopropanation 75 cyclic carbonates 12, 414, 417, 418, Ag-carbenoid enone 425 cyclopropanation 444 cyclic 1,2-diazine 69 alkene cyclopropanation 442 cyclic 1,3-diketones 88, 581, 633 diazoacetate effects 443 cyclic five-membered carbonate 415 diazoacetates 441 cyclic trifluoromethyl ketimines 50 enantioselective cyclopropanation cyclizations 759 441 domino and tandem reactions 583 mechanochemical conditions 441 [2+1] cycloaddition 74–77, 669 cyclopropanols 256, 296, 339 [2+2] cycloaddition 59–60, 78 cyclopropenation [2+2+1] cycloaddition 73–74, 78, 669 donor/acceptor-substituted diazo cycloaddition reactions 33–79 esters 441 [3+2] cycloadditions N-nosylhydrazones 443 azides 53–59 cyclopropyl carbinol rearrangement azomethine ylides 34–46 173 [3+3] cycloadditions 60–63 cytochrome P450 monooxygenases [4+1] cycloadditions 77 271 804 Index

d 2-diazo-3,5-dioxo-6-ynoates 160 Danishefsky’s diene 67, 69, 70, 534, diazonium salts 288, 306, 310, 312, 367 592, 633 6,6-dibenzannulated spiroketals 682 decarboxylative alkenylation 199 dibenzocycloheptadienes 253 decarboxylative alkynylation 19–20, 1,3-dicarbonyl compounds 234, 239, 197–199, 340, 341 345, 352, 546 decarboxylative azidation 215, 386 1,2-dichloroethane (DCE) 160, 202, decarboxylative bromination 218, 709 218, 305, 729 decarboxylative C–H arylation 354 Diels–Alder cycloadducts 516 decarboxylative chlorination 216, 217, Diels–Alder reaction 63–69, 72–73, 258, 376, 377, 709, 710 277, 516 decarboxylative C–S cross-coupling 1,3-diene 63, 65, 67, 68, 163, 508, 516, 395–396 522 decarboxylative direct C2-alkylation dienoates 513 342 difluoroamidation 234 decarboxylative etherification 206 difluoromethylated arenes 221, 306, decarboxylative fluorination 22, 23, 374 dihydrobenzofurans 155, 241, 288, 218–220, 226, 228, 258, 289, 333, 760 294–296, 373, 374, 472 dihydrofuran 74, 121, 122, 149, 162, decarboxylative nitration 215 165, 581, 583, 622 3,4-dehydroproline amide derivatives 2,5-dihydrofurans 149, 151, 620, 669, 118 677 δ1-or δ2-pyrrolines 48 dihydrofuroquinolinones 240 δ1-pyrrolines 46 dihydroisobenzofuran derivatives 431 δ3-pyrrolines 119 1,2-dihydroisoquinolines 123, 124, Deoxo-Fluor 274 139, 583, 670, 679 desilylation reaction® 435 dihydronaphthofuran products 162, deuterium labeling experiments 458, 163 463 dihydropyridines 60, 92 diaryl diselenides 202, 397 1,2-dihydropyridines 92 2,5-diaryl-3-hydroxypent-4-ynoic acids 3,6-dihydro-2(1H)-pyridones 121 156, 157 dihydropyrrole 108, 121 diaryliodonium bromides 370, 371 2,3-dihydropyrroles 48, 568 [4,5-diaryl-2-(2-(prop-2-yn-1-yloxy) dihydroquinolinones 352 aryl)-1H-imidazoles] 116 3,4-dihydroquinolin-2(1H)-ones 352 diaryl selenides 395 1,2-dihydro-2,2,4-trimethylquinoline diastereo-and enantioselective derivatives 384, 385 Ag-catalyzed azo-Diels–Alder 1,4-diketones 335 reaction 71 4,6-dimethoxy-2,5- diastereomeric epoxides 518 quinodihydrochalcone 340 1,2-diazine 69 4-dimethylaminopyridine (DMAP) diazines 274, 275, 372 415, 665, 780 diazoamide 366, 450 1-(2,2-dimethylcyclopropyl)methyl diazo compounds 13–14, 58, 59, 74, ketones 100 127 2,2-dimethylcyclopropylmethyl ketones involved reactions 364–367 360 Index 805 dimethylethylenediamine 302 alkyne-tethered cyclobutanols 593 dimethylsulfoxide (DMSO) 17, 185, cyclization 583–589 216, 238, 243, 255, 315, 319, 321, Mannich reaction 589–592 410, 749 Michael addition 574–579 2-diphenylphosphino-N,N-diisopropyl- ortho-alkynylaryl aldimines and carboxamide 54 indoles 585 (diphenylphosphoryl)silver 391 domino hydroamination/semipinacol 1,3-dipolar cycloaddition 39–45, 54, rearrangement reaction 593 85, 554, 555, 557–565, 567, 569, domino Michael/cyclization reaction 571, 573, 664, 669, 670, 685 568, 570, 574, 633 disilver core 379 donor–acceptor cyclopropenes 62, 4,6-disubstituted 2-aminopyrimidines 626 221, 222 double-decarboxylative cross-coupling 2,3-disubstituted-1,2-dihydro- 340, 344 isoquinolin-1-ylphosphonates 126 e 3,4-disubstituted (E)-β-B(dam)acrylates 43 dihydroquinolin-2(1H)-ones electrocyclic reactions 99–100 235, 245, 352 electron-deficient pyridines 358 1,4-disubstituted electrophilic silver-catalyzed 1,2-dihyroisoquinolines 124 fluorination 279–287 1,3-disubstituted furo[3,4-b]indoles electrospinning deposition 730 104 elemental silver 1 2,4-disubstituted γ-carbolines 130, 132 1,4-disubstituted imidazoles 48 enamides 202, 394, 395 α 1,3-disubstituted isoquinolines 130, enantioenriched -aminoallenes 118 131 enantiomerically enriched 2,3-disubstituted pyrroles 362 dihydropyranones 146, 147 2,5-disubstituted pyrrolines 108 enantiomeric silver-catalyzed 2,5-disubstituted 3-pyrrolines carbostannylation of alkynes 92 119, 120 enantioselective Mannich cyclization 1,4-disubstituted-1,2,3-triazoles 51 55, 58 enantioselective N-and O-nitroso-aldol 1,4-disubstituted 1,2,3-trizole 57 synthesis 13 2,6-di-tert-butyl-4-methylphenol (BHT) enantioselective nitroso aldol reaction 741 12–13 1,6-diyne compound 411, 413 5-endo-dig cyclization 108–110, 112, 1,6-diyne-4-en-3-ol 95, 96 145, 348, 570, 592, 613 1,3-diynes 310, 332, 612, 675 6-endo pyrones 156 1,6-diynes 95 enolate intermediates 431, 432 domino and tandem reactions enolate-sequential cyclization Aldol reaction 579–583 431–435 aliphatic aldehydes, 4-en-1-one intermediate 360 o-thiomethyl-p-anisidine, and enones 35, 59, 60, 423, 424, 441, 444, Danishefsky’s diene 592 680, 729 alkyl 2-formylbenzoates and 2-en-4-yn-1-azides 144 allyltrimethoxysilane 593, 594 enynes 90–94, 612, 675 806 Index

1,4-enynes 423 fluorinated isoquinolines 123, 286 1,6-enynes 90, 243, 246, 318 fluorinated oxazolidin-2-ones epoxide-propargylic esters 153, 154 250, 293 epoxides reduction fluorinated product 279, 413, 544 Ag NPs/HT-catalyzed epoxide fluorination reactions 22–23, 219, deoxygenation 756 272–274, 279, 280, 372, 374, 413 hydrotalcite (HT) 756, 757 fluoroalkylation of thiols 205 hydrotalcite-supported Ag 757 fluoroarylation of styrenes 226, 227, isopropanol 756 288, 289 nitro compound reduction 757–759 4-fluoro-2,5-dihydropyrroles 22, 120 3,4-epoxybut-1-ene production (EpB) 5-(fluoromethyl)-4,5-dihydroisoxazoles 733 229, 292, 293 ester 13, 40, 43, 95, 195, 276, 344, 408, 5-fluoromethyl-substituted γ-lactams 441, 458, 534, 669, 676, 679, 680, 291 691, 706 fluticasone propionate 219, 374 ethoxycarbonyldifluoromethylation formamides 194, 383, 384, 423 191, 192, 307, 367, 368 4,6-substituted ethylene oxide (EO) 4, 724 pyrrolo[3,2-d]pyrimidines 110, 2-ethynylanilines 688 111 ethynyl carbinols 17, 386 4-substituted benzofurans 165 evelynin 256, 340 5-substituted tetrazoles 55 (E)-vinyl sulfones 363 fulvenes 33, 60, 61, 240 exo-alkenyl cyclic carbonates functionalized propiolic acids 369 12, 418 functionalized quinolin-2(1H)-ones exo-cyclic alkenes 419 236 5-exo-dig cyclization 12, 92, 93, 102, functionalized silver nanoparticles 103, 105, 129, 144, 147, 163, 165, (FnAgNPs) cycloaddition 57 418, 431, 432, 435, 575, 670, 671, 2-furanones 435 708, 759 furanopyrimidine nucleosides 159 5-exo tetronic acids 156 furans 90, 92, 145, 168, 196, 239, 241, exo-trig cyclizations 116–118 335, 336, 350–352, 387, 679 5-exo-trig vinyl-substituted furoquinoline 159, 160 tetrahydrofurans 152 fused bicyclic pyrrolidine 36, 559

f g Feringa’s phosphoramidites 39 γ-allenoic acids 153, 158 ferrocene-based ligand Taniaphos 41 γ-allenols 153, 154 ferrocenyloxazoline-based N,P-ligand gem-difluoroalkenes 201, 308, 367, 369 40 gem-difluoromethylenated 5-and 6-endo-trig cyclizations phenanthridine 348 118–122 Glaser coupling 332 5-membered cyclic carbonates 422, glycyl sultam 43, 44 423 Grignard reagents 14–15, 201, 397, 5-substituted 1H-tetrazole 56 398, 407, 491, 665, 674 fluorinated imines 45, 46 guanidine 103, 104, 122 Index 807 h 5-methyl-substituted siloxyfuran halide ion scavengers 183 535 1-haloalkynes 375 5-methyl-substituted halogenated 2-arylpyrrole natural trimethylsiloxyfuran 538 products 109 o-thiomethyl-p-anisidine-derived halogenophilicity 7 imines 535 heteroarenes 191, 192, 194, 196, 197, S-containing N-aryl group 536 207, 209, 256, 257, 303, 313, 342, tert-leucine-bearing phosphine 540 357, 359, 371, 372, 384, 387, 388 H-pyrazolo[5,1-a]isoquinolines 135, heteroaromatic acids 185, 186 138–140 heteroaromatic substituted Huisgen 1,3-dipolar cycloaddition 1-ethinylcyclobutanols reactions 53, 85 297 Hunsdiecker halodecarboxylation 216 heteroaromatization reaction of Hunsdiecker reaction 216, 376, propargylic alcohols 171, 172 709–710 heteroaryl phosphonates 387 2-hydrazinopyridine 71 hexadehydro Diels–Alder reactions hydrazones 100, 123, 134–141 72–73, 277 hydroalkoxylation 99, 144–155, 575, 1H-isochromene derivatives 161, 679, 621, 622 682 hydroazidation of alkynes 16–17, 391 homoallylic carbamates 379, 474, 702, hydroboration 281, 668 705, 706 hydrocinchonine 41, 555 (homo)propargylic alcohols 104 hydrodifluoromethylation 224, 225 homopropargylic diols 146, 147 hydrofunctionalization 707–709 Hosomi–Sakurai allylation 435 hydrogen peroxide to propylene oxide Hoveyda–Snapper catalysts (HPPO) 727 alkyl-substituted aldehydes 534 hydrotalcite (HT) 738 alkyne-substituted aldimines 539 hydrotrifluoromethylation 224, 313, α-ketimine esters and 314 trimethylsiloxyfuran 537 hydrotrifluoromethylthiolation of aryl/alkynyl aldimines and alkynes 231 5-methyl-substituted 2-hydroxychalcone 65 trimethylsiloxyfuran 538 hydroxyfluorination 229, 287, 288 aryl/alkynyl aldimines and 4-hydroxy-5H-furan-2-ones 432 N-Boc-2-(trimethylsiloxy)pyrrole hydroxylamine derivatives 108 539 3-hydroxy pyrrolidine 43 chiral α-amino carbonyl compounds 4-hydroxyquinolin-2(1H)-one and derivatives 534 derivatives 428, 429 chiral α,β-unsaturated 2-hydroxystyrenes 164, 586, 587, 680 δ-amino-γ-butyrolactams 539, 540 cyclohexylcarboxaldehyde 540 i enantioselective vinylogous Mannich imidazo[1,2-a]pyridine derivatives 141 reactions 535, 540 imidazole-pyrrolones 143 iso-leucine-derived phosphine ligand 2-imidazolines 51, 52 538 imidazopyridines 192, 338 808 Index

iminotropones 61 isoquinolines 96, 106, 107, 113, 123, indanes 252 126–131, 133–135, 143, 161, 162, indanone-fused cyclohexene derivatives 237, 286, 678 163 isoquinolinium-2-yl amide 135, 139, 1-indanones 227 670 indoles 16, 67, 94, 97, 101, 105, 111, 113, 134, 156, 193, 194, 210, 228, 287, 352, 359, 360, 366, 370, k 583–585, 626, 627, 678, 683, 688, keto-enamides 89 759 ketones 2, 34, 47, 88, 202, 283, 333, indoline-fused cyclopentanone 99 424, 505, 552, 645, 670, 742 indolo[2,1-a]isoquinolinones 252 kinetic isotope eﬀect (KIE) 208, 355, intermolecular Ag-catalyzed amination 479, 489 381 Kolbe–Schmitt reaction 407 intermolecular C(sp3)–H amination kuwanon and dorsterone derivatives 213 65 intermolecular minisci arylation 195 intramolecular annulation 677–678 l intramolecular aziridination 471–474 lactate 44 intramolecular carbostannylation of lactones 36, 153, 157, 159, 171, 208, alkynes 91 285, 355, 413, 431, 551, 605, 606, intramolecular C–H amidation 212, 677 213, 465, 485, 700 Langlois reagent 223, 234, 338, 348 intramolecular hydroamination Lewis acid 4, 7, 33, 59, 66, 88, 99, 122, alkenes 122 153, 183, 239, 260, 331, 407, 744, alkynes 102–116 746, 750, 780 allenes 116–122 Lewis acidic transition metal-catalyzed intramolecular minisci arylation 195 cyclization reaction 416 intramolecular O-arylation 208 ligand-controlled and site-selective iodonium salts 312, 673 silver-promoted C–H amination 5-iodo-1,4-substituted triazoles 383 303 ligand-controlled site-selective isochromenylium 68 intramolecular C(sp3)–H isocyanide–alkyne cycloaddition amination 214 17–18 ligand-free Ag(I)-based bifunctional isocyanide-coordinated silver chelate catalytic system 410 51 ligustilide 156 isocyanide-involved reactions lithiated methoxyallene 362–364 121, 149 isocyanides 17, 18, 48, 52, 53, 59, 73, 74, 171, 172, 209, 237, 238, 354, 362–364, 570, 574, 601, 633 m 2-isocyanobiaryls 237 magnesium 344, 730 isonitrile 143, 237, 347, 348, 379, 408, malyngolide 158 581, 702 Mannich reaction 4, 533–554, 675 Index 809

domino and tandem reactions nitroalkenes 598–599 589–592 minimum energy crossing point Me-Duphos ligand 566, 567 (MECP) 75, 480, 481, 483, 503, Meldrum’s acid 166, 167 694, 695, 700 metal-catalyzed nitrene transfer Minisci reaction 188, 194, 195, 197, reaction 342, 360 bis(oxazoline) (BOX) and salen-type miscellaneous reactions 74–78, ligands 465 100–101, 362–371, 624–632, hypervalent iodine reagents 468 686–688, 711–713 intra-and intermolecular monofluoroethenyl cyclopentanones aziridinations and C–H 297 amidations 465 multi-substituted α,β-unsaturated mechanistic features 470–471 γ-lactones 170, 171 N-dentate bipyridine and multi-substituted tetramic acid phenanthroline ligands 468 derivatives 429 N-dentate ligands 468 münchnone intermediate 46 nitrogen sources 470 types 464 X-ray crystal structures 468 n metallocarbenes 440, 443, 445, 447, N-acyl amino acids 206 449, 668, 691 N-alkyl substituted δ3-pyrrolines 118 methaniminium chloride 334 N-alkyl-substituted δ3-pyrrolines 118 4-methylene-2-oxazolidinones 1, n-allenynes 94 102 nanoparticles 3, 23, 56, 57, 79, 369, methyltrimethoxysilane/3-mercaptopro- 377, 410, 419, 420, 596, 597, 655, pyltrimethoxysilane hybrid films 723–782 731 naphtho[b]cyclopropane 61 Meyer–Schuster type reaction naphthoquinones 188–190, 240, 342, 422 575 Meyer–Schuster type rearrangement naphthyridine product 123 423, 424 N-arylacrylamides 234, 244, 345 Michael addition N-benzylidene aniline 69 α,β-unsaturated carbonyl compounds N-cyclized imidazolidin-2-one product α,β-unsaturated esters and aryl 102 boronic acids 597 N-fluorobenzenesulfonimide (NFSI) arylidene/alkylidene malonates and 111, 120, 123, 124, 218, 229, 230, glycine Schiff base 595 274, 283, 285, 287, 458 β-ketoesters 595 N-heterocyclic carbene 2-cyclohexenone 596 polymer-supported silver heterogeneous chiral nanoparticles nanoparticle catalyst 410 596 N-heterocyclic carbenes (NHCs)

arylidene diphosphonates and glycine [AgOTf(IMes)2](IMes = Schiﬀ base 599, 600 1,3-bis(2,4,6-trimethylphenyl) domino and tandem reactions imidazol-2-ylidene) 662 574–594 bis(catecholato)diboron 662, 663 heteroaryl substituents 601 borylation reactions 667–668 810 Index

N-heterocyclic carbenes (NHCs) nitrogen/carbon-tethered (contd.) indolylcyclopropenes 100 carbene transfer, with diazo N-methyl-2-pyrrolidone 302 compounds 668–670 (–)-N-methylwelwitindolinone C CO2 insertions isothiocyanate 379, 702 allenylmethylamines 667 N–N bond formation 1,3-bis(4-methylbenzyl) minimum energy crossing points imidazol-2-ylidene silver (MECPs) 503 chloride 666 N-amidation and aziridination 4-dimethylaminopyridine (DMAP) pathways 503 665 N,N-di-Bocprotected propargylic alcohols 665, 666 6-amino-5-iodo-2-methyl A3-coupling reaction pyrimidin-4-ol 105 alkynylation of (non-)substituted N,N-diisopropylethylamine 552, 603, isatin 665 609, 647, 670, 760 alkynylation substituted isatin N-(2-perfluoroalkyl-3-alkynyl) 665 hydroxylamines 108 1-cyclohexyl-3-arylmethylimida- N-propargylic β-enaminones 92, 93 zolylidenes (CyNaph-NHC)AgX N-propargylic hydrazones 100 664 N-(prop-2-yn-1-yl)pyridin-2-amines 1,3-dipolar cycloaddition reactions 141, 142 664 N-tosyl aldimines 547, 549–551, 675, propargylamines 663, 664 1-[2-(pyrazol-1-yl)phenyl] 677 imidazole 664 N-tosylaziridines 632 cyclization reactions 670–671 N-tosylhomopropargylamines 108, homogeneous and heterogeneous 109 catalysts 662 N-tosylpyrroles 108 hydroboration 668 N-trifluoroethylation 458, 459 organosilver complexes 673–674 N-(2,2,2-trifluoroethyl)imines 43 oxidation of alcohols 672 nucleophile-addition products 72 semi-hydrogenation of alkynes nucleophilic reagents 123, 309–313, 672–673 315, 546 N-hydroxyphthalimide (NHPI) 735 nucleophilic silver-catalyzed nitration of olefins 214, 215, 385 fluorination 274–278 nitrene transfer reactions 20–22, nucleophilic trifluoromethylthiolation of 464–467, 471, 474, 481, 503, 504, alkyl chlorides 315 694–696 N-unprotected THIQs 398 nitrile hydrolysis 724, 776–778 nitroalkenes 41, 45, 555, 564–568, 574, 575, 577–579, 598–600, 633 o nitroaminoxylation 232, 233 o-alkynylacetophenone 431, 433, 680 nitroarylation 249 o-alkynylaryl aldehyde oxime derivatives nitro-containing compounds 345 129, 130 nitrogenation of terminal alkynes o-alkynylbenzaldoximes 130, 131 18–19 o-(1-alkynyl)benzamides 166, 167 nitrogen-based 1,3-dipoles 34 (o-alkynyl)phenyl enaminones 167, 168 Index 811 octahydropyrrolo[3,4-c]pyrroles 39, oxazolidine-2-ones 102 560 oxazolidinones 102, 117, 419, 421, 424, o-cyclized oxazolidin-2-imine products 426, 431 103 oxidative arene cross-coupling 15–16 o-heterocycles 148 oxidative coupling olefins 214, 215, 385, 508–513, 563, azo coupling 775–776 695 C–H oxidation 772–775 aziridination 694, 699, 700, 705, 706 cyclization reactions 344–356 one-electron Ag(I)/Ag(II) redox cycles oxidative cross-coupling 8, 335–344, 8 390, 391 1,n-allenynes 94–95 oxidative-induced C–H 1,n-diyne compounds 95–96 functionalization 335–344 1,2,5-and 1,2,3,5-substituted pyrroles oximes 129–134, 229, 292 109 oxindole framework 359 o-nitrobenzoic acids 212, 216 oxirane synthesis 669 Oppolzer sultam 43, 44 oxo-and azaphilic character of silver 7, o-propargylcarbamates 102, 103 33 o-propargylic hydroxylamines 107 2-oxobutenoate 48, 49 optically active δ-aminoallene 116 oxy-anion intermediate 415, 417 organic azides 215, 386 oxyfluorination 229, 292, 293 organic nucleophilic fluorinating reagents 273–274 organoborane compounds p 189 panduratin 64, 65, 78 organoboronic acids 190, 357, 629, para-quinone methides 680 630 parent amines 383, 384 organotrifluoroborates 344 P-containing oxindoles 347 ortho-alkynylaryl ketones 586, 679 Pd/Au/Ag trimetallic nanoparticles ortho-alkynyl salicylaldehydes 68, 585, 767 586, 678, 679 Pd-catalyzed Buchwald–Hartwig ortho-anilines 746 amination 742 ortho-perfluoroalkylation 307, 368 peptide-derived ligand 67 ortho-trifluoromethylation 191, 306 perfluoroalkylated compounds oxa-and aza-Diels–Alder reactions 367–368 67–72 perfluoroorgano silver compounds oxametallacycle (OMC) intermediate nucleophilic reagents 309–313 725 precursors 304–309 oxamic acids 166, 197 perfluoroorgano silver(I) compounds 1,4-oxathian-3-imine derivatives 172, 272, 300 173 phenanthridines 237, 244, 247, 248, oxazine/benzoxazine-fused 347, 348, 352, 353 isoquinolines and naphthyridines phenols 130, 145, 155, 171, 197, 208, 127 361, 687, 770 1,4-oxazine derivatives 153, 154 phenyl vinyl diazoacetates 458 oxazoles 50, 104, 107, 237, 354, 707 phosphatyloxy alkynyl ketones 168, oxazolidin-2,4-diones 250, 293, 294 169 812 Index

phosphine ligand 10, 41, 164, 186, 334, polysubstituted 1,6-dihydropyridazines 468 100 2-phosphinobenzo[b]phosphole oxides polysubstituted furans 239, 350–352 248 polyvinylpyrrolidone (PVP) 740, 776 phosphinoxzoline (PHOX) 39 porphyrins 440, 447, 465, 468 6-phosphinoylated phenanthridines potassium benzoate derivative 414 347 precursors 2, 34, 102, 188, 298, 304, 3-phosphonated coumarin derivatives 344, 414, 445, 564, 666 350 primary amines 89, 116, 120, 126, 355, phosphonation reaction 389 421, 575, 748 phosphonoarylation of alkynes 245 primary Csp3–H bonds 381, 701 phosphonoﬂuorination 228 prochiral N-(2-t-butylphenyl) phosphonylated azaspiro[4,5]decenones maleimide 39 254 prolinamide 39 phosphonylated ﬂuorenes 246, 247 propargyl alcohol 11, 90, 92, 315, 417 phosphonylated 1-indenones 247 propargylamides 169 3-phosphonylated indoles 247 propargylamines 10, 102, 332, 333, 6-phosphonylated phenanthridines 417, 424, 429, 610 248 propargyl benzoates 152 phosphonylation propargyl bromide derivative 411, 413 of alkenes 232, 249 propargyl compounds 96–98 of alkynes 232, 233 propargylic amides 165, 166, 670, 671, phosphonylimines 50, 51 708, 709 1-phosphorylated isoquinolines 133, propargylic ureas 102, 103 134 propargyl-tethered pyridines 141 photoredox catalysis 183 propiolamide 91, 197

Ph2P(O)Ag intermediate 345 propiolic acid derivatives 408, 411 4-picolinoyl pyrroles 51 propylene oxide (PO) 724, 727 π-Lewis acid 4 2-propynyloxy-6-fluoropyridines 142 plasmon-mediated Ag NPs catalysis protodecarboxylation 9–10, 184–186, catalyst reduction 771 207 LSPR in coinage metal nanoparticles of carboxylic acids 9–10 768–770 Pschorr-type cyclization 344 oxidation 770–771 purine nucleosides 188, 189, 196 photocatalysis, silver halides for 772 putative silver ion-chelated dipole 34 P,N -bidentate ligand pyranoquinoline rings 160 (S)-TF-BiphamPhos 37 pyrans 155 poly(acrylic acid) (R = H) 295 pyrazoles 108, 690 polycyclic benzo-fused dihydrofurans pyrazolo[1,5-a]pyridines 110, 111, 135 169, 170 pyrazolo-isoquinolines 135, 139, 141 polycyclic carbazoles 241 pyrazolones 89, 202, 578 polycyclic compounds 126, 162, 240 pyrazolopyrido[4,3-d]pyrimidines 135, polycyclic heterocycles 126 138 polyheterocycles 164 pyridazines 149, 187 polyoxometalates (POM) 732 pyridine-N-oxides 192, 193, 196, 342 polystyrene-supported N-heterocyclic pyridines 64, 104, 194, 274, 357, 372, carbene silver complex 420 470, 620, 670, 671, 696 Index 813 pyridinones 252 decarboxylative fluorination pyrido[1,2-a]pyrimidin-4-ones 122 294–296 pyrido[2,3-d]pyrimidines 105, 107 fluorination via addition to alkenes 2-pyridyl alkynyl carbinol 51 287–294 pyrimidines 110, 159, 188, 189, 342 rearrangement/migration/C–C bond 2-pyrones 435 cleavage pyrroles 17, 51, 52, 67, 92, 97, 108, 118, aryl migration 249–255 119, 121, 126, 160, 191, 209, 238, radical C–C bond cleavage of 241, 335, 348, 362, 387, 559, 707 cycloalkanols 255–259 pyrrolidines 34, 36, 39–45, 78, 381, representative silver-catalyzed 383, 554, 556, 557, 559–562, 566, utilization of carbon dioxide 613, 620, 700, 701, 713, 745 408 pyrrolidin-3-one derivatives 96 resveratrol 241 3-pyrrolines 88, 116, 119, 120, 707 ring-opening addition to alkenes 256 pyrrolobenzodiazepine skeletons 192, ring-opening chlorination and 193 bromination 258 ring-opening trifluoromethylthiolation 258 q [Ru(dppp)2(CH3CN)Cl][BPh4]- catalyzed homocoupling 332 4-quinazolinones 247 quinolines 188, 195, 274, 275, 333–335, 342, 360 s quinones 67, 188, 189, 191, 192, 256, (S)-BINAP-based catalyst 36 257, 339, 340, 357, 359, 395 S-(difluoromethyl) quinonyl aryl thioethers 395 benzenesulfonothioate

(PhSO2SCF2H) 204–205 secondary γ-aminoallenes 117 r Selectfluor 22, 111, 218, 274, 287, 372 racemic α-allenic alcohols 151 Selectfluor 274 radical addition selenylation® 202, 203 C–C bond formation 222–228 sequential binary catalytic [3+3] C–heteroatom bond formation cycloadditions 62 228–233 seven-and eight-membered rings 157, 3 radical benzylic sp C–H fluorination 158 298 𝜎-Lewis acid 4 radical C–C bond cleavage of Si–H functionalization 461 cycloalkanols 255–259 silacyclopropanes 75, 76, 504–506, radical coupling 508, 512, 522 C–C bond formation 187–202 silanols 724, 778–780 C–halogen bond formation silica gel column chromatography 678 216–222 siloxyalkynes 59, 69 C–N/P bond formation 209–216 silver C–O/S/Se bond formation 202–209 acetylides 5, 11, 17, 18, 52, 54, 172, radical silver-catalyzed fluorination 232, 233, 239, 333, 334, 349, 352, C–C bond activation 296–297 362, 363, 391, 407, 408, 410, 665, C–H bond activation 297–298 673, 766, 767 814 Index

silver (contd.) domino and tandem reactions alloys 739–742 574–594 applications 3–4 Friedel–Crafts reaction 626, 627 carbonate 51–53, 302, 370, 371, 375, Mannich reactions 533–554 383 Michael reactions 595–601 carboxylate 185, 294, 376, 410, 414 N-tosylaziridines 632 chemistry of 1–2 spirocyclization strategy 630 dicyanamide/diisopropylethylamine silver-catalyzed carbon phosphorylation 55 of alkenes 345 nanoparticles 3 silver-catalyzed C–H insertion reactions silver-activated aryne 72 365 silver catalysis silver-catalyzed Csp2–H C–H alkynophilicity/carbophilic nature of trifluoromethylation 337 silver 4–6 silver-catalyzed Csp2–H chemoselective cyclopropanation functionalization/C–O 13–14 cyclization 355 A3coupling reaction 10–11 silver-catalyzed cyclization reactions decarboxylative alkynylation 19–20 α-aryldiazoketones 169, 170 enantioselective nitroso aldol reaction Brønsted acid catalysis 85, 104 12–13 Conia-ene reaction 86–89 fluorination reactions 22–23 cycloisomerization 89–98 halogenophilicity 7 cyclopropyl carbinol rearrangement homocoupling of alkyl Grignard 171, 173 reagents 14–15 electrocyclic reactions 99–100 hydroazidation of alkynes 16–17 6-endo-dig cyclization/nucleophilic incorporation of CO2 11–12 isocyanide-alkyne cycloaddition addition 144 17–18 heteroaromatization reaction of nitrene transfer reactions 20–22 propargylic alcohols 171, 172 nitrogenation of terminal alkynes Huisgen 1,3-dipolar cycloaddition 18–19 reactions 85 oxidative arene cross-coupling hydroalkoxylation 144–155 15–16 hydrocarboxylation 155–159 oxo-and azaphilic character of silver intramolecular hydroamination 7 102–122 protodecarboxylation of carboxylic miscellaneous reactions 100–101 acids 9–10 multi-substituted α,β-unsaturated silver-catalyzed anti-Markovnikov γ-lactones 171 hydroxyfluorination 288 1,4-oxathian-3-imine derivatives silver-catalyzed asymmetric reactions 172, 173 allenes 534, 619–622 polycyclic benzo-fused dihydrofurans allylation 534, 616–619 169, 170 amination reaction 534, 623–624 silver-catalyzed decarboxylative azabenzonorbornadienes, acylation 342, 343 ring-opening reaction of 631 silver-catalyzed decarboxylative Conia-ene reaction 628 alkynylation 19, 20, 197, 340, 1,3-dipolar cycloaddition 554–574 341 Index 815 silver-catalyzed decarboxylative ethyl glyoxylate, phenylalanine arylation 361, 362 ethyl ester, and maleimides 560 silver-catalyzed decarboxylative 2H-pyrroles and polysubstituted chlorination 376, 377 pyrrole derivatives 561 silver-catalyzed 1,3-dipolar L-tert-leucine amidophosphane cycloaddition 563 glycine imino esters and (S)-TF-BiphamPhos-type ligand α,β-unsaturated carbonyl 559 compounds Xing-Phos ligand 561, 562 chiral mono-and biphosphine silver-catalyzed double Csp3–H ligands 555 cross-coupling 335 glycine imino esters and nitroalkenes silver catalyzed fluorinated quinoline α-substituted imino esters 564 synthesis 334 α-imino γ-lactones 566, 567 silver-catalyzed intermolecular MonoPhos and Phosferrox ligands amination 379, 500 567 silver-catalyzed intermolecular phosphoramidite ligand 564, 565 fluoroarylation 288 ThioClickFerrophos ligand 566 silver-catalyzed intramolecular Xing-Phos ligand 565 carbocyclization 360 isocyanoacetates and α,β-unsaturated silver-catalyzed intramolecular carbonyl compounds 568–572 fluoroarylation 289 isoquinolinium/phthalazinium silver-catalyzed Mannich reactions methylides and enecarbamates alkenyl trichloroacetates 552, 553 573 α,α-dicyanoolefins 549, 550 silver-catalyzed 1,3-dipolar α,β-diamino methyl esters 547 cycloadditions α-sulfanyl lactones 550, 552 α-imino ester 554 β-dicarbonyl compounds 547 azomethine ylides 554, 555 chiral α,α-disubstituted α-amino acid glycine imino esters and derivatives 552 α,β-unsaturated carbonyl chiral quaternary α,β-diamino acid compounds derivatives 550 AgOAc and ferrocenyl chiral ligand 548 (S)-TF-BiphamPhos-derived glycine Schiff base 547, 548 ligand 560 imino glycine alkyl esters 547 α-silylimines and pyrone-based isatin-based ketimines 553, 554 trisubstituted olefins 563 N-aryl aromatic aldimines and azomethine ylides 558 alkenyl trichloroacetates 553 chalcones 556, 557 N-tosyl aldimines 550, 551 cyclopentene-1,3-diones 558 N-tosyl aldimines and oxazolones diethyl maleate 563, 564 551 2,2-dimethoxyacetaldehyde- N-tosyl aryl aldimines 548, 549 derived glycine imino esters Vinylogous Mukaiyama–Mannich 563 reactions, Hoveyda–Snapper electron-deficient and catalysts 534–546 electron-neutral substituents silver-catalyzed nitrene transfer reaction 557 21 816 Index

silver(I)-catalyzed oxidative cyclization Tpx-silver complexes 378 (trispyrazolylborate ligands) silver-catalyzed oxidative dearomatiza- carbene transfer reactions tion/cycloisomerization/Michael 690–693 addition cascade 165 nitrene transfer reactions silver-catalyzed oxidative 694–696 homodimerization of free silver-coordinated isocyanide 48, 52 indoles 360 silver(I) fluoride 272, 273, 300, 301, silver-catalyzed oxyfluorination 293 303, 307, 308, 367 silver-catalyzed perfluoroalkylations silver(I) hexafluoroantimonate 272 313–314 silver-mediated and catalyzed silver-catalyzed phosphonofluorination trifluoromethylthiolations 291 aliphatic carboxylic acids 322 silver-catalyzed phosphorus nucleophilic trifluoromethylthiolation carbocyclization 351 of alkyl chlorides 315 silver(II)-catalyzed pharmaceutically and agrochemically protodecarboxylation 186 relevant molecules 314, 315 silver-catalyzed radical silver-catalyzed tandem aminofluorination 292 trifluoromethylthiolation/aryl silver-catalyzed radical migration 320 carbofluorination 289, 290 Sonogashira coupling reaction 317 silver-catalyzed tandem 3-trifluoromethylthiolated coumarins trifluoromethylation 348 318, 319 silver-catalyzed three-component trifluoromethylthiolated coupling 332 1,2-dihydronaphthalenes 321 silver-catalyzed transmetalation 397, silver(I)-mediated and 398 silver(I)-catalyzed fluorination silver-chelated aldehyde 67 272 silver-complexed ferrocenyl N,P-ligands silver-mediated carbene transfer 40 reactions, Wolff rearrangement silver complexes, in organic reactions 439 arylated fluoroalkyl halides silver-mediated Csp2–H 711, 712 trifluoromethylation 336 chiral silver phosphates 674–688 silver-mediated A3 coupling reactions 711, 713 Csp3–trifluoromethylthiolation NHC silver complex 662–674 393 P,O-type silver complexes 688–689 silver-mediated decarboxylative C–N pyridine-containing ligands coupling 215 aziridination vs. C–H amination silver(I)-mediated fluorination 698–706 electrophilic silver-catalyzed carbene insertion 706–707 fluorination 279–287 Hunsdiecker reaction 709–710 medicinal applications 273 hydrofunctionalization 707–709 nucleophilic silver-catalyzed twelve-membered fluorination 274–278 pyridine-containing ligands organic nucleophilic fluorinating (Pc-Ls) 710–711 reagents 273–274 Index 817

radical silver-catalyzed fluorination silver alloys 739–742 287–298 alkene epoxidation silver-mediated oxidative vinylic C–H ethylene oxide (EO) 724 bond sulfenylation 394 propylene oxide (PO) 727 silver-mediated perfluoroalkylations styrene epoxidation 729–733 301–313, 324, 367 alkynes reduction 754–755 silver-mediated trifluoromethylation alkynylations 298–314, 336, 337 alkyne coupling to carbon dioxide silver-mediated 765–766 trifluoromethylation-iodination alkyne cross-coupling 767–768 309 A3 coupling 761–765 silver nanoparticle-catalyzed cyclizations 759–761 carboxylation 410 carbonyl reduction silver nanoparticles acetalization and catalyst alcohol–alcohol coupling 748–750 deactivation 752 alcohol oxidation acrolein hydrogenation 751 acrolein 740 α,β-unsaturated aldehydes 752 aerobic alcohol oxidation C=C reduction 750 735–737 cellulose nanocrystals (CNC) 753 alcohol–amine coupling 742–748 crotonaldehyde hydrogenation alcohol dehydrogenation 752, 753 737–739 stoichiometric conditions 750 alcohol deprotonation and oxygen unsaturated carbonyl 750 adsorption 741 epoxides reduction 755–757 Au/Ag bimetallic alloy clusters Lewis acid 780–781 740 nitrile hydrolysis 776–778 Au/Ag nanotubes (Au/Ag NT) oxidative coupling 741 azo coupling 775–776 benzylic and aliphatic alcohols C–H oxidation 772–775 733 plasmon-mediated Ag NPs catalysis β-hydride elimination 733, 734 catalyst reduction 771 continuous gas phase 736 LSPR in coinage metal enthalpy of reaction 734 nanoparticles 768–770 HT-catalyzed dehydrogenation oxidation 770–771 738 photocatalysis, silver halides for mechanism 733–735 772 M–H bonds 733 silanol chemistry 778–780 Misono’s classification 734 silver(I) nitrate 110, 145, 272, 286, 287, nanoporous 308, 322 chitosan/polyacrylamide silver-promoted azomethine ylide interpenetrating polymer cycloaddition 34 networks 739 silver-promoted fluorination 293, 294 1-octanol oxidation 737 silver-promoted tautomerization 52 pathways and side reactions 735 [silver(I)(pyridine-containing ligand)] Sanderson’s classification of complexes 333, 710 transition metal oxides 734 silver tosylate (AgOTs) 14 818 Index

silver(I) triflate 272 1-(2-(sulfonylamino)phenyl)prop-2-yn- silver(I) trifluoroborate 272 1-ols 104 silylene transfer reactions 6-sulfonylmethylated phenanthridines allenes 522 244 allylic silanes 522 sulfur-centered radicals 230 allylic sulfides 522, 524–525 surface-enhanced Raman spectroscopy carbonyl compounds 513–518 (SERS) studies 741, 768 C–O bonds 518–521 symmetric prochiral bispropargyl copper-based complexes 504 alcohols 420 diastereomeric allene derivatives 519 monosubstituted silacyclopropanes t 505 tandem 1,3-acyloxy migration/5-exo-tet olefins 508–513 cyclization 97 π-bond insertion reaction 505 tandem 1,3-acyloxy 1,2-regioisomer 506 migration/Mannich-type silacyclopropanes 504 addition/elimination 97 silyl-protected 2-naphthols 69 Taniaphos 41, 43, 562, 563, 623 site-specific C–P coupling 212 tautomer 127, 363 solvent-corrected Gibbs free energy terminal alkynes 5, 11, 17–19, 52–54, profiles 352 56, 135, 162, 231, 237, 239, 277, Sonogashira coupling 317, 767, 768 335, 349, 375, 408 sp2-hybridized carbon-silver bond terminal epoxides 408, 414–416, 665 413, 414 tethered indolylcyclopropenes 101 spirocyclic indolenines 682 tetrahydrofurans (THF) 74, 152–154, spirocyclic scaffolds 97, 98 535, 619, 620, 622, 669, 677, 690, spiro[indoline-3,4′-piperidine] 691 derivatives 100, 101 tetrahydroimidazoles 45, 46 spiropyrazolones 89, 577 tetrahydroisoquinolines 366 spiropyrrolidines 34–36 tetrahydronaphthol 64 styrenes 202, 210, 211, 214, 223, 224, tetrahydroquinoline derivatives 701 226–232, 287–289, 291, 388, 474 1,2,3,4-tetrahydroquinolines 381, 701 epoxidation 729–732 tetramic acid derivatives 429 substituted α-allenic alcohols 150 tetramic acids 429, 430 substituted indoles 209, 387, 584 tetrasubstituted alkenes 156, 157, 441, substituted indolizines 349 588, 589 substituted propargyl acetates 169 tetrasubstituted furans 90, 168, 335, substituted propargyl 336 acetates/pivaloates 168, 169 1,2,4,5-tetrasubstituted imidazoles sulfamates 212–214, 378, 470, 471, 356 474, 484, 613, 698 tetrasubstituted pyrrolidines 36 sulfenylation 202, 203, 394, 395 tetraynes 72 sulfinyl chiral auxiliary-based tetrazoles 55–57, 146 diastereoselective cycloadditions tetronic acids 149, 156, 432, 434, 435 45 thermally allowed cycloaddition sulfonimidamide 695 reactions 33 Index 819 thermally stable tricyclic xanthines 113 1,3-bis(2,6-diisopropylphenyl) trifluoromethylated aromatic imidazol (idin)ylidene compounds 336 NHC-ligated difluoromethylated trifluoromethylated pyrrolidines 43 silver complexes trifluoromethylating reagent 310,

[(NHC)AgCF2H] 311 336–338 thiazoles 188, 189, 209, 256, 342, 387, trifluoromethylation-iodination of 389, 390 arynes 309, 310 ThioClickFerrophos (TCF) 40, 566 2-trifluoromethyl-1,3-enynes 120, 121 thiolation 204, 242, 395 trifluoromethylfluorination 226, 227 thioureas 103 1-(trifluoromethyl)-4-fluoro-1,2- three-component reaction of propargyl dihydroisoquinoline 124 alcohols, carbon dioxide, and trifluoromethyl ketones 147, 149, 225, nucleophiles 421–422 309, 368, 369, 765 3D-supramolecular coordination trifluoromethyl reagent 345 polymers (SCP) 58 trifluoromethyl silver complex 302 1-((2-tosylamino)aryl)but- 3-trifluoromethylthiolated coumarins 2-yne-1,4-diols 104 242, 318, 319 1-tosylhydrazon-4-oxy-5-ynes 135, trifluoromethylthiolated 136, 140 1,2-dihydronaphthalenes 243, tosylmethyl isocyanide (TosMIC) 171, 321 363, 364, 574, 601 trifluoromethylthiolating reagent 204, 4-tosyloxyisoquinoline 130, 133 395 Tp *,BrAg 379, 380, 477, 495–497, 503, trifluoromethylthiolation reagent 322, 694, 695 345 trans-dioxasilacyclononenes 515 trimethyl(2-methylenebut-3-yn- transition metal-based Lewis acid 1-yl)silane derivatives 435 33 trimethylsilyl chlorodifluoroacetate transition-metal-catalyzed C–H (TCDA) 303, 304 functionalization 331, 407 tri-or tetrasubstituted furans 90 transition metal-catalyzed radical triphenylphosphine 166, 506, 588, 628, reactions 183 760, 764 transition metal-catalyzed versatile 1,4,5-trisubstituted 2-aminoimidazoles coupling reactions 331, 407 103 trans-metal-catalyzed decarboxylative trisubstituted benzenes 100, 360 coupling 342 1,2,4-trisubstituted benzenes 100 triazenes 191, 192, 196, 306, 307, 367, 1,2,5-trisubstituted 1H-imidazoles 368 127 1,2,3-triazoles 55, 56, 157 1,4,5-trisubstituted imidazoles 53 1,2,4-triazoles 187 two-electron Ag(I)/Ag(III) redox tricarbonylmethanes 364 chemistry 8 tricyclic benzo[f ]imidazo 2-substituted [1,2-d][1,4]oxazepine derivatives 4H-pyrido[1,2-a]pyrimidin- 116 4-ones 122 tricyclic piperidines 60 2,3-/2,3,4-substituted pyrroles 52 tricyclic scaffolds 114, 344 2,3-substituted indoles 127, 129, 210 820 Index

u cyclohexylcarboxaldehyde 535, unactivated alkanes 213, 335 540 unactivated alkenes 154, 155, 211, enantioselective vinylogous 224–229, 232, 255, 289–293, 313 Mannich reactions 535, 536, unactivated alkynes 17 539 unactivated Csp3–H bonds 392–394 iso-leucine-derived phosphine unsaturated amine derivatives ligand 538, 540 424–426 5-methyl-substituted siloxyfuran unsaturated amines 428–430 535 unsaturated heterocycles 516 5-methyl-substituted unsymmetrical diaryl ketones 343 trimethylsiloxyfuran 538 urea-based diazene 71 o-thiomethyl-p-anisidine-derived imines 535 S-containing N-aryl group 536 v tert-leucine-bearing phosphine vinyl acids with alkynes 237 540 vinyl diazoacetate reaction 462 N-benzyl fluorinated aldimines 543 vinylene carbonates 418 N-Boc aldimines and vinyl epoxides 518, 520, 521 trimethylsiloxyfuran 544 Vinylogous Mukaiyama–Mannich 5-vinyl oxazoles 169, 170 reactions vinylpyrrole 63 aromatic N-aryl aldimines 541–543 vinyl trifluoromethyl sulfides 231, and trimethylsiloxyfuran 253 541–543 with trimethylsiloxyfuran 544–546 w chiral α-amino carbonyl compounds Wolff rearrangement 439 and derivatives 534 Arndt–Eistert synthesis 439 chiral fluorinated aldimines and α-diazo-β-ketoesters 439, 440 trimethylsiloxyfuran 544 mechanism 439, 440 chiral phosphine-oxazoline ligands 541, 542 chiral phosphine-Schiff base type y ligands 541 ynamides 59, 60, 77, 78, 94, 135, 277 2,4-dimethoxy group 541 ynone-tethered pyridine-, isoquinoline-, fluorinated aldimines 542–544 and pyrazine 143 Hoveyda–Snapper catalysts alkyl-substituted aldehydes 534 alkyne-substituted aldimines 539 z chiral α,β-unsaturated (Z)-2-alken-4-ynoic acids 156 δ-amino-γ-butyrolactams 539, (Z)-2-methylene-1-sulfonylindolin-3-ols 540 104