Subject index a acoradiene absinthin 278 – acid-catalyzed cyclization to cedrene 236 – wormwood, isolation from Artemisia acorane–cedrane interconversion 237 absinthium L. 277 acoranes acetic acid – biogenetic relationship to zizaenes 255 – synthesis of 42, 921 acrylates – dianion of 301 – reduction of, with magnesium in methanol acetic acid side chain 442 – by alkylation of ketones 314 acrylic acids – mild hydrolysis of 698 – hydrogenation of 111 a-acetoxy ketone acyl anion equivalent – reduction of, with zinc 546 – generation of 862, 864 acetylation – in maytansine synthesis 857 – lipase-catalyzed 440 acyl anion synthons 188 (+)-acetylcephalotaxine 656 acylation acetyl-CoA 802 – of enamine with mixed anhydride 662 – in biosynthesis of cephalotaxine N-acylhomomeroquinene 534 esters 657 acyliminium cyclization 579 acetylenes acyloin condensation 661 – hydroboration of 379 – Ruhlman modification 662 acetylgynuramine 619 acylpyridines 3-acetyl-2-piperideine – hydrogenation of 771, 784 – acylation with methyl chloroformate 770 3-acylpyridines – by hydrogenation of 3-acetyl-pyridine 770 – hydrogenation to vinylogous amide 592 3-acetylpyridine – in general method of synthesis 195, 196, – hydrogenation of 592, 593, 770 593 – in indole alkaloid synthesis 195, 196, 771, 3-acylpyridinium salts 776 – acid-catalyzed cyclization of 593, 782 aconitine 530, 531, 847, 848 – in alkaloid synthesis 195, 196, 592 The Way of Synthesis. TomÐ Hudlick and Josephine W. Reed Copyright 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 978-3-527-31444-7 958 Subject index N-acyl vinylogous urea – of keto ester dianion 435 – attachment of, in palytoxin synthesis 901 1,4-alkylative dearomatization Adam’s catalyst 260, 375, 376, 397, 609, 626 – in cedrene synthesis 234 – hydrogenation of limonene 399 alkylative transposition aflatoxin 847 – of 1,3-carbonyl 664 aflatoxin B1 846 alkyl zinc b-agarofuran – addition to ketone 484 – synthesis 113 – in quassin synthesis 484 AIDS Alloferine 801 – treatment of 910 allyl ether ajmalicine 541, 542, 761 – reductive fission of 299 – in biosynthesis of indole alkaloids 762 allylic alcohols ajmaline 541, 542 – by reduction of malonates 316, 317 alcohol dehydrogenase – directed hydrogenation of 512 – in desymmetrization of meso diols 117 – from epoxides 485 alcyonin 5 – oxidation with MnO2 317 – structure revision 4 – reductive transposition of 488 aldehyde synthesis – by reduction of epoxy mesylates 317 – by hydrolysis of gem-dichloride to 782 allylic bromination 383 aldolase allylic carbamate displacement 741, 742 – in enzymatic aldol condensation 116 – suprafacial 742 aldol condensation 48, 292, 451, 453, 462, 664, – with lithiosilanes 741 766 allylic epoxidation 508 – asymmetric 55, 56 allylic oxidation 400, 472, 474, 476, 477, 509 – in damsin synthesis 305, 306 – chemoselective 310 – intramolecular 306, 583, 776 – of 1,4-diene to dienone 786 – in aspidospermidine synthesis 776 – of olefin to enone 556, 785 – in zizaene synthesis 261 – with 1,3-oxygen shift 352 – transition state model 57 – with retention of olefin regiochemistry alexine 639, 641 588 alizarin – with selenium dioxide 591 – synthesis 41, 42 p-allylnickel complex 319 alkaloid allyloxycarbonyl (ALOC) – origin of the word 527 – reduction of 182 alkaloids 5 allylsilane cyclization – chronology of isolation 528 – of acylimminium ion 627, 743 – general methods of synthesis 767 Amaryllidaceae constituents b-alkoxygenone synthesis 854 – bibliography 721 alkylation – biological acitivites of 689 – a vs. c control 168, 259, 260 – biosynthesis of 689, 691 – C vs. O control 168 – isolation 689 – C vs. O vs. N control 168 – structura 689 – of carbonyl compounds 167 – synthesis of ent-series 720 – of crotonates 167 ambrosin 278 a-alkylation americanolide 278 – of enone 511 amide reduction – of unsaturated ester 608 – via imino chloride 633 a-alkylation vs. c-alkylation amino cyclitols – of enones 259, 260 – synthesis of 155 Subject index 959 amino hydroxylation 58 – isolation from Cephalosporium aphidicola – asymmetric 641 Petch 449 aminoindanol – isolation from Nigrospora sphaerica 449 – from indane cis-diol 912 – synthesis of 104 (+)–(S)-amphetamine 529 – total synthesis, Corey 455 amphidinolide B 871 – total synthesis, Holton 105, 461 – synthesis of 869 – total synthesis, Ireland 456 (+)-amphidinolide W – total synthesis, McMurry 451 – synthesis of 869 – total synthesis, Trost 451 – revision of structure 871 D-arabinose amprenavir 911 – Kiliani–Fischer chain extension 24 – HIV-I protease inhibitor 910 – proof of stereochemistry 25 androsterone 208 arboflorine 849, 850 anionic cyclization arborescin 278, 295 – of alkoxides to enynes 293 arene–olefin cycloaddition 241, 389, anionic oxygenation 390, 420 – of benzylic carbon 540 – in retigeranic acid synthesis 400 anionic rearrangement – photochemical 372 – of imino esters 633 – in cedrene synthesis 239 a-anion synthons 188 aromadendrene 277, 278 anisole (–)-aromadendrene 325 – demethylation of 735 aromatic dihydroxylation 136 – oxidative cleavage 576, 579 aromatic substitution annopodine 574 – photostimulated 663 annotine 574 aromatin 278 annotinine 574 aromatization 854 – synthesis of 588 aspartyl protease – Wiesner’s synthesis 590 – inhibition of 911 [4+1] annulation 104, 406 aspidoalbine 760 – intramolecular of dienic aspidophytine 780 diazoketones 403 – total synthesis, Padwa 779 [3+2] annulation Aspidosperma alkaloids 761, 763, 764, 820 – in triquinane design 363 – approaches to 775 ansa compounds – general method of synthesis 769, 770, 772, – definition of 879 773, 776, 794 – history of 879 – structure elucidation 780 ansomytocins 851 – chemical interconversion of 764 antascomicin A 871 aspidospermidine 530, 760, 761, 764, 770, 772, – synthesis of 869 773, 776, 780, 794, 815 antascomicin B 871 – bibliography 826 1,4-anti elimination – conversion to vincadifformine 773 – of HBr, in diene synthesis 443 – disconnection analysis 765 aphidicolin 213, 449, 453, 454, 455, 463 – total synthesis, Aube 773 – asymmetric formal synthesis of 461 – total synthesis, Heathcock 775 – bibliography 464 – total synthesis, Kutney 775 – biogenetic-type synthesis 456 – total synthesis, Magnus 775 – biological activity of 449 – total synthesis, Schultz 786 – biomimetic approaches to synthesis 451 – total synthesis, Wenkert 767 – disconnection analysis 450 – total synthesis, Zard 775 960 Subject index (–)-aspidospermidine – synthesis 244 – asymmetric synthesis of 786 – radical cascade of 243, 246 aspidospermine 531, 759, 760, 780, 921 azulene – bibliography 826 – from oil of chamomile 277 – comparison of Stork’s and Ban’s intermediates 767, 768 b – dehydrogenation with zinc dust 31 baccatin III 13, 499, 500 – disconnection analysis 765 – esterification of 507 – Emde degradation of 34 – symmetry-based design 151 – fragmentation of 32 Baeyer–Villiger reaction 118, 308, 309, 321, – Hofmann degradation of 34 485, 555, 556, 557, 560, 579, 705, 720 – isolation from Aspidosperma quebracho – asymmetric 59 blanco 764 – Hudrlik silicon-directed version 785, 786 – oxidation of 32 – in eburnamonine synthesis 786 – structure proof 23, 31 – in quassin synthesis 483 – total synthesis, Stork 765 baker’s yeast reduction – Xray structure 32 – of keto esters 639 Asteraceae families of plants barbatusol 488 – source of pyrrolizidine alkaloids 617 Barton–McCombie deoxygenation 246, 381, asymmetric oxidation 54, 110, 112, 117, 118 383, 388, 404, 409, 419 asymmetric reduction 110 Barton reaction 112 – of enones 667 Baylis–Hillman reaction 578 – with chiral oxazaborolidine catalysts 110, – of ethyl acrylate with 488, 667 m-methoxybenzaldehyde 577 atom economy 96, 727 Beckmann rearrangement 47, 48, 595, 800 – definition of 97 – in ibogamine synthesis 799 atom transposition – of dihydrocodeinone oxime 30 – in cyclic compounds 176 – Barton nitrone version 311, 313 atropine 529, 531 benzene atropoisomerism – chemical oxygenation of 119 – in vancomycin 873 – synthesis from acetylene 214 – in pancratistatin synthesis 698 – asymmetric dihydroxylation of 118 australine 639, 641 benzocyclobutane (+)-australine – cycloreversion 114 – total synthesis, Denmark 639 – in steroid synthesis 209 azabicyclo[3.3.0]octane 619 benzyl ether – disconnective strategies 620 – deprotection with BBr3 352 aza-Diels–Alder reaction N-benzoylmeroquinene 537 – in daphnilactone synthesis 609 o-benzyloxime 709 azadiene formation 609 benzyne alkylation aza–ene reaction – intramolecular 661 – of acylimminium ion 627 benzyne generation azaspiracid-1 6 – with sodium or potassium amide 663 – structure revision 5 Bergman cycloaromatization aza sugars – of ene-diyne subunit 873 – synthesis of 155 Beyermann–Grewe cyclization 737 azide–diene cycloaddition 636 bicyclic ketones N-aziridinyl imine – stability relationships in 177, 179, 180, – in radical cyclization 267 181, 279 Subject index 961 bicyclo[2.2.1]heptane bis(dihydroquinidino)–phthalazine – fragmentation of 308 – in asymmetric amino-hydroxylation 641 – in hydrazulene synthesis 307 1,2-bis(trimethylsiloxy)cyclobutane 663 bicyclo[2.2.2]octanone Bohlman–Wenkert bands – via a Diels–Alder reaction 560 – IR frequencies 576 bicyclo[2.2.2]octene – in structure elucidation of heterocycles – cleavage of 484 575 bicyclo[3.2.1]octanone bond-set analysis 130 – synthesis of 463 Boraginaceae families of plants bicyclo[3.2.1]oxaoctane – source of pyrrolizidine alkaloids 617 – in phorbol synthesis 470, 471 (–)-borneol 507, 517, 518 bicyclo[3.3.1]nonanone Bredt’s rule 588 – synthesis of 586 brevenal 874 bicyclo[3.3.0]octanes – biological activity