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Index a alkoxide addition 88 N,S- structure 346 – diastereoselective C-O formation a-acetoxy thioderivative 138 b-alkoxy vinyl 95 acidity 323, 351f., 362, 377 alkoxy-lithium aluminium hydride 57 acyclic synclinal model 296 O- sulfinate 33f. acyl anion equivalent 161f. O-alkyl arene sulfinate 37 – -stabilized 162 O-alkyl p-toluenesulfinate 39 N-acyl 314f. O-alkyl tert-butanesulfinate 39 acylation 212f. alkyl carbinol 62 1-adamentylsulfinamide 239 alkyl carrier 225 ADC, see asymmetric dipolar cycloaddition alkyl ferrocenyl sulfoxide 286 1,4-addition 90, 125 alkyl sulfinamide 237 addition-elimination-isomerization (AEI) – ketimine 240 reaction 219 – sulfinyl aldemine 240 1,4-adduct 294 – tertiary 237 33f., 38, 203, 210 a-alkyl-b-ketosulfoxide 61f., 71 – anti-1,2-amino 302 – reduction 71 – homoallylic 219f., 286 alkylation 70ff., 136, 287, 354ff., 357, – homopropargylic 220f. 389f. – secondary 203, 272, 305 – base influence 356 – sulfinylation using cinchona alkaloid/ – cyclic sulfonyl sulfoxide 357 arenesulfinyl chloride system 38 – Pd-catalyzed 287 – b-sulfonimidoyl-substituted 219f. – b-phenylsulfinylethanol 356 – d-sulfonimidoyl-substituted 219 – solvent influence 70 131, 133, 187, 279, 295, 302, – stereochemical course 389 363, 365f. – stereocontrol 354ff. – cyanosilylation 279 – vinyl sulfoxide 356f. – a,a-heterodisubstituted 142 alkylidencylopentane 96 – a-hydroxy 302 alkylidene transfer 214 – Zn-promoted allylation 131 alkylsulfinyl group 236 aldol reaction, see also Michael-aldol 201 reaction 73, 169f., 227 all-carbon stereogenic quarternary – Cu(I)-catalyzed 74 center 294ff. alkaloid 36 allenic derivative 202 alkane sulfinate 37, 46 allocyathin 313f. alkanesulfinyl chloride 49 p-allyl complex 278f. alkenyl 292ff., 309 allyl cyclopropane 94 alkenyl sulfoxide 88 g-allyl intermediate 279 2-alkenyl sulfoxime, titanated N-methylated – M-type 279 219 – W-type 279

Organosulfur Chemistry in Asymmetric Synthesis. Edited by Takeshi Toru and Carsten Bolm Copyright 6 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim ISBN: 978-3-527-31854-4 418 Index

allyl sulfide 336 – b-functionalized 189 allyl sulfone 301 b-amino 244, 258 allyl sulfoximine 216 a-amino 246 g-allyl system 279 b-amino ketone 244, 248 allyl transfer 216 – syn-a-substituted 248 allylation 286, 299, 381f. a-amino 246 – aldehyde 286 amino sulfoxide 80 – a-sulfonyl carbanion 381f. (6R,7S)-7-amino-7,8-dihydro-a-bisabolene – a-sulfonyl-stabilized 299 257 – sulfoxide-promoted 286 b-aminophenylpropionic acid 371 allylic alcohol 62f. 1,2-aminothioether 134 allylic alkylation reaction 254, 273, 276 Andersen method 3f., 237 – 1,3-diphenyl propenyl acetate 273 Andersen reagent 235f. – Pd-catalyzed 254, 273f. anion-stabilization effect 163 allylic amination 276 anthracyclinone 78, 139 – Pd-catalyzed 276 – precursor 139 allylic substitution 273ff., 278 l-arabinitol 59 – enantioselectivity model 278 arene sulfinate 37, 46 – mechanism 276ff. arenesulfinyl chloride 49 – Pd-catalyzed 273f., 278 aromatic aldehyde 183 allyltitanium(IV) complex 203 aromatic sulfoxide 131 – in-situ-formed sulfonimidoyl-substituted – ortho-directed metallation 131 203 O-aryl alkane sulfinate 33f. aluminium (salalen) complex 20 O-aryl arene sulfinate 33f. AM1 calculation 401 aryl carrier 225 130 aryl methyl sulfoxide 20 – a,b-unsaturated 130 aryl sulfinamide 237, 240 amide enolate addition 248 – ketimine 240 a-amido sulfone 315 – sulfinyl aldemine 240 203, 233, 235, 241 – tertiary 237 – primary 241 arylation 21 – secondary 203 N-arylation 213, 222 – stereoselective 233 – Buchwald-Hartwig-type 213 – synthesis 233, 241 – metal-catalyzed 213 amino acid 89, 246f., 259, 297 arylboronic acid addition 246f. – a,a-disubstituted 297 – rhodium-catalyzed 246f. a-amino acid 89, 246, 259, 366 – rhodium(I)-phosphine-catalyzed 246 – cyclic 366 trans-arylcyclopropane carboxylate 195 – substituted 246 arylimine 134, 368f. – a-trifluoromethyl 370 O-arylmethyl tert-butanesulfinate 35 amino acid ester 221 a-arylpropionic acid 174f. amino alcohol 39, 90, 303 arylsulfinamide 237 – anti-1,2-disubstituted 1,2-amino – biocatalytic route 237 alcohol 133 arylsulfinyl group 236 1,2-amino alcohol 242f. 2-(arylsulfinylmethyl)oxazole 366 1,3-amino alcohol 244f. arylsulfonyl group 293 – Nelson’s asymmetric synthesis 245 a-arylthio amide 332 1,4-amino alcohol 244f. aryltitanium reagent 293 – mechanism 246 asymmetric dihydroxylation (AD), – synthesis 244 see dihydroxylation a-amino alcohol 243 asymmetric dipolar cycloaddition (ADC) b-amino alcohol 90, 140, 369 111ff., 115 g-amino alcohol 140 – 1,3-ADC 113, 115, 117, 118 amino compound 189 – p-facial selectivity 111 Index 419

– non-functionalized vinyl sulfoxide 111 benzylidenation 183ff. asymmetric substitution 275, 277 N-benzyloxycarbonyl b-(fluoroalkyl) – Pd-catalyzed 275, 277 b-enamino sulfoxide 82 asymmetric transformation, see betaine 183, 186f., 191f., 196f., 403f. transformation – cisoid 191f. aza-Darzens reaction 190, 249f. – formation 183, 187, 191, 196 aza-Darzens-type chemistry 249f. – reactivity 403 aza-Wittig reaction 81 – rotation 404f. azabicycle 219 – structure 404 azaheterocycle, functionalized 217 – transoid 191f. azapolycycle 217 bicyclo[4.1.0]heptanes 312 aziridination 189ff., 192f., 249ff., 252, 405 bicyclo[2.2.2]octene 108 – catalytic 192 binaphthol 15 – diastereoselectivity 190 biologically active compound 176, 256ff., – mechanism 190f. 322, 336 – stereoselectivity 250f. – synthesis 256ff. – stoichiometric 190 biomimetic model 409 aziridine 92, 134, 180, 189ff., 192f., 214, Bolm catalyst 19 249ff., 252 bond strength 237 – application 249 borane 203 – aza-Darzens-type chemistry 249f. – tetrasubstituted 203 – formation 191 borohydride 57, 67, 69 – ring-opening 189 boschnialactone 103 – synthesis via methylide 251 Brook-type rearrangement 164 aziridine-2-phosphate 249f. bryostatin 176 aziridinyl carboxamide 190 Buchwald-Hartwig conditions 222 azomethine ylide 115ff., 119, 300f. tert-butanesulfinamide (t-BSA) 236f., 239, – heteroatomic 117 242, 248, 250f. axially chiral olefin 335f. – enantiomerically pure synthesis 239 – synthesis 237, 239 b tert-butanesulfinate 51 B3LYP calculation 400ff., 403f., 410, 414 N-tert-butanesulfinyl aziridine 251f. benzaldehyde 126, 183ff., 272f., 360f. tert-butanesulfinyl imine 243 – diethylzinc addition 272f. tert-butyl alkyl sulfoxide 6 benzenesulfenate 51f. tert-butyl arylsulfinate 6f., 35 – oxidation 52f. 1,2-bis(tert-butyl) disulfide 406f. – ortho- group bearing 52 tert-butyldimethylsilylcyanide (TBDMSCN) benzenesulfinate 51ff. 82 – ortho-phosphonate group bearing 51f. tert-butylsulfinamide 256 benzimidazolyl vinyl sulfone 299 tert-butylsulfinate 9 O-benzyl tert-butanesulfinate 35f. tert-butylsulfinyl group 236 – synthesis 36 benzyl tert-butyl sulfinate 6f., 35f. c benzyl tert-butyl sulfoxide 23 C-a control 77 benzyl phenyl sulfide 333ff. C3 triethanolamine ligand 15 – a-lithiated 334 CaC bond formation 225, 227 – transition state 334 – metal-catalyzed 225, 227 benzyl 2-pyridyl sulfide 336ff. cage compound, heterocyclic 125 benzyl sulfide 342, 344 calyculin 176 N-benzyl a-sulfinyl imine 80 carbacycline 336 benzylamine 85 339 benzylic alcohol 141 carbanion 163, 214, 321ff., 330f., 351ff. benzylic carbanion 133, 135f., 141 – configurational stability 330f. benzylic chiral center 136 –(R,M)-configured 395 420 Index

carbanion (cont.) – energy 402 –(S,P)-configured 395 – stability 401 – conformation 334, 352, 375f. – structure 401f. –SE2 reaction 334 conjugate addition 56, 83ff., 86ff., 125, 132, –sp2-like hybridized 334 167, 224, 292ff., 295f., 307, 344, 357ff. – stabilization 163, 214, 326, 339 – 1,4-conjugate addition 132 – sulfonimidoyl-stabilized 214 – benzylamine 85 carbinol 59, 61f., 72, 110, 269f., 273, 360, – enantioface-selective 344 364 – general principle 83f. – cyclic 63 – Grignard reagent 88 carbocycle 96 – intramolecular 86f. (–)-N-carbomethoxypelletierine 112 – intramolecular one-pot deprotection carbonyl ylide 121 process 86 carboxylation 362f. – malonate 357 – prostereogenic a-sulfinyl carbon 362 – Ni-catalyzed 84, 224 88, 345 – nucleophilic 84, 86 – b-alkyl-substituted 88 – radical-promoted 83, 95 – a-hydroxy 345 – Rh-catalyzed 294f. catalyst 12, 16, 18f., 225ff., 252ff., 255f., – stereocontrol 357f. 267ff., 270f., 276, 281, 283, 285, 287f. – a-sulfinyl carbanion 357ff. – 279 – thiolate 85 – dual Lewis-acid-Lewis-base 288 – a,b-unsaturated carbonyl compound 296 – heterogeneous 285 – a,b-unsaturated ester 358 – reusable 285 – a,b-unsaturated sulfoxide 83ff. – P,N-sulfinimine-based 256 – vinyl sulfone 294 (–)-centrolobine 66 conjugate reduction 297f. cetirizine 259ff. – Cu-catalyzed 298 – synthesis 259ff. – b,b-disubstituted a,b-unsaturated (S)-cetirizineHCl 260f. carbonyl compound 297 chair transition state 165, 362, 368 – b,b-disubstituted a,b-unsaturated chalcone 224f. sulfone 298 chelation control method 171 contact-ion pair 376ff., 379, 388, 394 a-chloro-a-sulfinyl carbanion 365f. – configuration 394 chlorosulfite 49f. – structure 394 O-cholesteryl 1-alkenesulfinate 44f. copper, see Cu O-cholesteryl methanesulfinate 44 CP-293,019 281 – synthesis 44 cross-coupling 221f., 226f. chromium complex 341ff. – metal-catalyzed 221f., 226 – deprotonation 343 – Ni-catalyzed 221 cinchona alkaloid 36ff., 296 – Pd-catalyzed 222, 226f. cinchona ester 37 crossed-aldol reaction 169f. cisoid 191f. – mechanism 169 (–)-cispentacin 115 – l-proline-catalyzed 170 CMO, see cyclohexanone mono-oxygenase crotylation 286 collidine 412f. – benzoyl 286 computational chemistry 399f. Cu catalyst 74, 200ff., 227, 252ff., 298, computational study 399ff. 301, 311f. condensation 41ff., 240f. Cu complex 200f. condensing reagent 42 Cu(MeCN)4PF6/bis(oxazoline) 201 configuration 323ff., 326, 330, 352 Cu(SbF6)2-SIAM 252ff. – inversion 338ff., 341 Cu(II)-SIAM catalyst 252ff. – retention 338, 341, 380 curcuphenol 89 conformation 98, 182, 352, 375f. Curtin-Hammett principle 204, 331 conformer 401ff. Curtin-Hammett situation 385 Index 421

N-cyano sulfoximine 212 – intramolecular 311f. cyanoacetate 296f. – mechanism 196f. – thiourea-catalyzed addition 297 – stoichiometric 195ff. cyanohydrin 128 – styrene 282 cyanosilylation 279 cyclopropane 94, 120f., 180, 194ff., 198, – Ti-catalyzed 279 214, 282 b-cyanosulfoxide 85 – synthesis 282 cyclization 95f. – trans 198 –5-exo-trig 95f. cyclopropyl ester 283 cycloaddition 56, 96, 103ff., 106, 122f., 270f., 292 d –[2þ 2] 292 DAG (diacetone-d-glucose) 5, 45ff., 409ff., –[2þ 2 þ 1] 123 412f. –[3þ 2] 292, 301 – stereoselectivity 412 –[4þ 2] 292 DAG alkylsulfinate 5 –[4þ 3] 122 DAG arylsulfinate 5 – catalytic 270f. DAG method 5, 409ff. – 1,3-dipolar 300 – mechanism 411 –5-exo-trig 96 – model system 410, 412 –6-exo-trig 96 – steric model 412f. – formal [2 þ 2 þ 1] 123 DAGOH 409f., 412f. –[5þ 2] intramolecular 122] Dane’s diene 99f., 106 – intramolecular radical 96 Darzens reaction 314f., 353 – Lewis acid-catalyzed 300 Davis’ method 237 – Pd-catalyzed 301 Davis’ protocol 246 – sulfinyl-directed [5C þ 2C] intra- DCG (dicyclohexylidene-O-glucose) 45ff. molecular 402 decarboxylation 382f. cycloalkanone 72f. 5,6-dehydropiperidin-2-one 360 cyclobutane adduct 169 3,4-dehydroproline 222 cycloheptenone 132 density functional theory (DFT) 399f., cyclohexadiene 104 404 cyclohexane 125 density functional theory/molecular cyclohexanone 310 mechanics (DFT/MM) 399 cyclohexanone mono-oxygenase (CMO) deprotonation 330f., 343, 381, 383ff., 393 172ff. deprotonation-quenching sequence 393 cyclohexene 125 desulfinylation 116f. cyclohexenol 63, 108 DET (R,R-diethyl tartrate) 12ff. cyclohexenone 125, 132 diacetone-d-glucose, see DAG cyclohexylamine 241f. a,a’-dialkyl-b-ketosulfoxide 62 – a-substituted 241f. diamine 242 – synthesis 241f. – C2-symmetrical vicinal 242 cyclopentadiene 98ff., 102ff., 105, 309 a,b-diamino acid 246 cyclopentane 122 a,b-diamino ester 242 – functionalized 122 diarylamine 247 2-cyclopentanone 91 a-diazo-b-keto ester 312 cyclopentene 359 a-diazo-b-ketosulfone 311ff. – functionalized 359 diazoacetamide 202 cyclopentenone 89, 91, 132 – substituted 202 – substituted 89 diazoalkane 118ff. cyclopropanation 93f., 179f., 194ff., 197f., diazocompound 188, 190, 201f. 281f., 311ff., 405 diazoester 200ff. – 194 DIBAL (diisobutylaluminium hydride) 57ff., – Cu-catalyzed 311ff. 60ff., 63ff., 66ff., 69f., 76, 79, 81, 124, – cycle 283 128f., 132 422 Index

DIBAL/ZnCl2 59f., 62ff., 65ff., 68ff., 71, disparlure 356 79, 129, 132 dithiane 161, 167, 169ff., 172, 344f. – reduction 59ff., 62ff., 65ff., 71, 76, 132 – conversion 161 – reduction mechanism 61 – crossed-aldol product 169f. – stereoselectivity 63ff., 66ff. – 2-hydroxy 164 DIBAL/ZnX2 59ff. – lithiated 162ff. dicyclohexylidene-O-glucose, see DCG 1,3-dithiane 161ff., 170, 344 Diels-Alder reaction 55, 96, 98ff., 101, – 2-anion 161 103ff., 109ff., 127, 130, 175, 227, 252ff., – a-carbanion 344 270ff., 308f., 401 dithiane oxide 171, 175 –[4þ 2] 175 1,3-dithiane ring introduction 162 – asymmetric hetero 109ff., 308 1,3-dithiane-1-oxide 171f., 174 – catalytic 271 dithioacetal 161ff., 167f., 171, 176f., 344f. – chiral Lewis acid-catalyzed 252, 271 – application 175 – Cu(SbF6)2-SIAM-catalyzed 252ff. – a-lithiated 167f., 344 – endo-attack model 272 – natural product 175 – hetero 127f., 227 double stereodifferentiation process 369 – intramolecular 108f. Doyle-Kirmse reaction 199 – Ti-promoted 308 dual activation 279, 281 diene 96, 98ff., 102ff., 106ff., 128, 252ff. dynamic kinetic resolution (DKR) 35, 331ff., – acyclic 253f. 334, 336, 394ff., 409ff. – cyclic 99, 252f. – energy diagram 332 – 4-methyl-substituted 128 – reaction pathway 332 dienophile 96ff., 99ff., 102ff., 107, 254, – sulfinyl chloride racemate 409 308 dynamic thermodynamic resolution 331, – bidentate 308 333f., 336, 338ff., 345 – cyclic 100 – energy diagram 331 – reactivity 97, 107 – reaction pathway 331 – stereoselectivity 97 – sulfinyl 97 e – vinyl sulfoxide 96 electron-density effect 369 diester 227 electron-withdrawing group 88, 97, 102f., R,R-diethyl tartrate, see DET 107, 121, 136, 236f., 292, 297, 300, 302, 2,3-dihydrofuran 220f. 314, 367, 401 dihydroxylation 301ff. electronic approach control 98 – a,b-unsaturated sulfone 302 electrophile 72f., 131, 135ff., 139, 180ff., – vinyl sulfone 302f. 203, 336ff., 342f., 353, 369, 371 diisobutylaluminium hydride, see DIBAL – activation 279 b,d-diketosulfoxide 64 – b-ketosulfoxide 73 (R)-(–)-2,6-dimethylheptanoic acid 174 – prochiral 182 diol 63, 64f., 129, 168, 302, 345f. – N-sulfinylimine 133, 135 – synthesis 63 electrophilic addition 96 1,2-diol 65 enaminonitrile 92 1,3-diol 64, 129 b-enaminosulfoxide 79ff. 1,3-dipolar reaction 55, 110, 117, 300f., – synthesis 79 403 enantiodetermining step 400 – calculation 403 enantioface-selection 344f. – Cu-catalyzed 301 enantiomerization barrier 377ff., 380 – cycloaddition 111, 117, 300f. enantioselection 399 – stereocontrol 403 – energy difference 399 dipolarophile 111ff., 120 endo approach 112 – activated vinyl sulfoxide 113 endo mode 98 – acylic sulfinyl acrylonitrile 120 endo/exo isomerization 393f. dipole 111, 121 – free activation energy 394 directing effect study 400, 403 endo/exo isomerization time 393f. Index 423 endo/exo selectivity 103, 105, 107, 111, furanone 113f. 113f., 116f., 120, 124, 238, 300 furyl imine 193 energy barrier 400, 403, 410ff. – translation into enantiomeric excess 400 g enolate 248, 358f. generalized gradient approach (GGA) 400 – addition 248 glycidic acid 78 – trapping with electrophile 358f. glycidic derivative 187 ephedrine 9 Grignard reagent 4, 6f., 9ff., 12, 70, 72, 88, epoxidation 181, 183, 186, 188f., 301, 94, 126, 171, 242, 244f., 261, 327, 364 303f., 404f. – dithiane oxide addition stereoselectivity – aryl aldehyde 404 171 – dienyl sulfone 303 guanacastepene 216f. – general scheme 405 – mechanism 404 h – rate-determining step 404 H/D exchange experiment 382 – 2-sulfonyl-1,2-cycloalkadiene 303 – mechanism 382 – a,b-unsaturated 303 (–)-halosaline 243 – vinyl sulfone 303f. a-halosulfone 314f. 58, 68, 74, 76, 163, 183, 186, 214, Heck reaction 223 314f., 353 helicenequinone 106 – aliphatic 186 heteroarylsulfone 292f. – functional 187f. Hoffmann test 325, 333 – ring-opening 163 homaline 94 – terminal 187 Horner-Wadsworth-Emmons (HWE) – unsaturated 186 olefination 302 a,b-epoxy sulfoxide 91 hybrid quantum mechanical/molecular epoxysulfone 314 mechanical calculation (QM/MM) 400, 412 (þ)-erythro-roccellic acid 90 hydrocyanation reaction 76ff., 82f., 85, 125, esomeprazole 14 128 ester 302, 359f. – mechanism 77 – g-hydroxy-a,b-unsaturated 302 – a-sulfinyl ketone 77 – a,b-unsaturated 358ff. hydrogenation 228, 255f., 267f., 270, 305f. Et2AlCN 76f., 83, 85, 125, 128 – biferrocene diphosphine Rh-catalyzed 306 – pentacoordinated 77 – chemoselective 228 ethane 1,2-bis-sulfinyl chloride 48 – imine 228 Evans auxiliary 11 – ketone 305 Evans oxazolidinone 12 – b-ketosulfone 305f. exo approach 113, 115 – olefin 255f. exo mode 98 – reactivity 228 external quench 380 – Rh-catalyzed 268 – Ru-catalyzed 305f. f 22 p-facial selectivity 97ff., 100, 103f., 106f., hydroperoxo complex 406f. 109ff., 112ff., 117ff., 120ff. b-hydroxide ketone 132 – control 106 a-hydroxy acid 90 fenoprofen 90 b-hydroxy acid 90 ferrocene 131 b-hydroxy sulfide 201, 333 ferrocenyl p-tolyl sulfoxide 12 b-hydroxy sulfone 305, 381, 388 flavone 89 a-hydroxy-carbanion equivalent 369 O-(9-fluorenyl) tert-butanesulfinate 35 b-hydroxy-g-ketoester 73 g-fluoro-b-iminosulfoxide 81 – a-substituted 73 fluoroalkyl imine 370 (2S,3R)-(–)-3-hydroxy-methylproline 166 formyl anion equivalent 167f. (E)-g-hydroxy-a,b-unsaturated sulfoxide 85 free ylide pathway 202 g-hydroxyalkylation 216f., 219 furan-2(5H)-one 302 a-hydroxyester 227 424 Index

b-hydroxyester 58, 73 j hydroxyethylamine dipeptide isostere 370 Jacobsen conditions 303 a-hydroxyketone 68, 175 Jacobsen’s catalyst 303f. hydroxysulfone 306ff., 381 Julia-Colonna procedure 304 hydroxysulfoxide 57f., 70 Julia-Kocienski olefination 294 b-hydroxysulfoxide 58f., 63, 272f., 356, 364 Julia-like olefination 297 – a-alkylation 256 Julia-type reaction 291, 315 – bidentate ligand 272f. – homoallylic 59 k b-hydroxysulfoximine 215, 224f. Kagan oxidation 13 hygroline 112 b-keto g-sulfinyl ester 65 hyperconjugation 163, 323ff., 333, 377f. – stereoselective reduction 65 hypervalent iodo compound 24 ketone 73, 183, 215f., 305, 307, 363 ketosulfone 305ff., 308ff., 315 i b-ketosulfoxide 57ff., 60f., 63ff., 66ff., 69ff., imination 212 73f., 77f., 80f., 117, 124f., 128f. – agent 212 –(SR)-a-alkyl-g-fluoro-ketosulfoxide 75 – metal-catalyzed 212 – electronegative influencing imine 81ff., 190, 192, 212, 228, 236, 240, chemo- and stereoselectivity 76 367ff. – fluorinated 69, 74 – diastereofacial selectivity 236 – hydrocyanation reaction 76, 125 – electronic nature 192 –(S)-g-monofluorinated 74 – hydrogenation 228 – perfluorinated a-alkyl(aryl) 76 – nitrogen substitution 236 – polyhalogenated 69 – protected 193 – reduction 57ff., 60, 63, 124f., 129 – substituent 193 – a-sulfenyl group influence 67 – a-sulfinyl carbanion addition 367ff. – g,d-unsaturated 59f. b-iminosulfoxide 79ff., 82, 360 (1R,SR)-ketosulfoxide 75 – arylation 82 kinetic conditions 113 – reduction 79 kinetic control 368 – synthesis 79 kinetic resolution 395, 397 indolizidine 79, 86 (R)-indolizidine 79 l induction 57, 283 lactam 169 – 1,2-induction 77, 326f., 329 b-lactam 127, 139, 194 – 1,3-induction 62f., 77, 80 lactone 59ff., 62, 65 – 1,4-induction 92, 124ff., 130, 167 – macrocyclic 60 – 1,5-induction 128, 130 g-lactone 61f., 364 – 1,6-induction 129 d-lactone 62, 357, 364 –1,n-induction 57 lactone enolate 73 – enantiodetermining pathway 330 Lewis acid 252, 271, 279, 300 – energy diagram 330 Lewis acid-Lewis base bifunctional – mechanism 283, 321, 329f. asymmetric catalysis 279f. – reaction pathway 330 ligand 14ff., 228, 252ff., 255, 265ff., intermolecular b-addition 95 268ff., 271, 273ff., 276, 279, 281, 283f., internal quench 380 287f., 305, 307, 312, 322, 368, 376, intramolecular C-H insertion 311 386f., 413 intramolecular hydride transfer 61, 70, 124 – bidentate 273f. intramolecular nucleophilic substitution –C1-symmetric 274f. 179 –C2-symmetric 1,2-diol 14 iron complex 19 –C3-triethanolamine 15 isomerization time 393 – carbohydrate-tethered sulfur 270 isoxazolidine 115 – chiral chelating 414 – 5,5-disubstituted 115 – coordination mode 266f. isoxazolopyridazinone 118 – enantioselectivity 275f., 279 Index 425 ligand (cont.) methyl phenyl sulfoximine 211, 224 – external ligand effect on stereoselectivity – preparation 211 369 O-methyl sulfinate 40 – hydroxysulfoxide 284 – steroidal 40 – immobilizing 307 – synthesis 40 – N-based 267 methyl p-tolyl sulfoxide 11f., 15 – phosphine-based 267 methylating reagent 70 – S,N 271, 275 methylation 354f. – sulfinamide-based P,N 255 – cyclic sulfoxide 355 – sulfoxide bonding mode 267 – stereocontrol 355 – sulfoxide-based 265ff., 274, 279, 287 – a-sulfinyl carbanion 355 – sulfoxide/nitrogen 275 a-methylene-g-lactone 355 – sulfoxide/phosphine 276f., 279 exo-methylenecyclopropane 301 – sulfoxime 228 methylenedithiolane 169 – sulfur coordinating role 414 – cycloaddition with chiral lactam 169 – thioether-based 288 methylidenation 187 – thioether/phosphorus 288 Metzner epoxidation 189 lithiated dithiane 162ff. Michael acceptor 292, 294, 357, 359 lithiated N-methyl sulfoximine 215 Michael addition 86, 89, 91ff., 94, 219, lithiation 322, 324 222, 294ff., 344, 360, 395 d-lithiation 220 – diamine-catalyzed 296 2-lithio-1,3-dithiane 162ff., 167 – intramolecular 86, 91 – aldehyde/ketone addition 164 – mechanism 92 2-lithio-2-methyl-1,3-dithiane 166 – organocatalyzed 295 2-lithio-2-phenyl-1,3-dithiane 165 – a-substituted cyanoacetate to vinyl lithium complex 73f. sulfone 296 – tricoordinated 73f. – transition state model 296 lithium enolate 73 Michael reaction 21, 86, 89, 91ff., 94, 219, 222, 294ff., 309ff., 344, 360, 395, 401 m Michael-aldol reaction 309ff. malyngolide 313f. – b-aryl a,b-unsaturated ketone 310 manganese catalyst 17 – catalyst function 310 manganese complex 17 – organocatalytic 310 manostatin 63 – working model 310 maytansine 364f. Mitsunobu reaction 69 menthol 3, 24, 41ff., 44 Modena system 13 – condensation with p-toluenesulfinic molybdenum complex 19 acid 41f. MP2 calculation 401 menthyl alkylsulfinate 4, 8, 42, 44 Mukaiyama reaction 127, 129, 227 menthyl arene sulfinate 42f. – aldol 127, 129, 227 menthyl sulfinate 4, 8, 42f., 44, 288 – vinylogous aldol 227 – synthesis 4 multicomponent coupling 164 O-menthyl p-toluenesulfinate 40 (MeO)3PO 354f. n metal-catalyzed asymmetric catalysis NaBH4 68, 79, 81 267ff. naphthaldehyde 126 metalloenamine 243, 257 – remote asymmetric nucleophilic methanesulfinate 5 trifluoromethylation 128 methyl alkyl sulfoxide 4 1-naphthyl methyl sulfoxide 19 methyl o-bromophenyl sulfoxide 17 nelfinavir 85f. methyl tert-butyl sulfoxide 23 neutral coordinate-organocatalyst 284 methyl carbinol 61 nitrile oxide 117f. methyl enol 75 nitro group reduction 226 methyl jasmonate 313f. nitrogen-activating group 237 methyl phenyl sulfoxide 16, 18, 23 nitrone 111ff., 114f., 119, 175, 371 426 Index

[3 þ 2] nitrone cycloaddition 175 p nucleophile 130, 137, 285 palladium catalyst 222, 226f., 254f., 273ff., – activation 279 276f., 278 – silicon-based 285 palladium-catalyzed asymmetric allylic – sulfinated 130 alkylation (Pd AAA) 273ff., 276 – ortho-sulfinated benzylcarbanion 132 (–)-pateamine 258f. nucleophilic addition 56ff., 84, 90, 133 – synthesis 258f. – intramolecular 133 Pauson-Kahn reaction 123 – Ni-catalyzed 84 – intramolecular 123 – a-sulfinyl group-mediated 57ff. Pd AAA, see palladium-catalyzed asymmetric nucleophilic epoxidation 91, 175 allylic alkylation nucleophilic process 123ff. Pd(p)-olefin p–complex 278 nucleophilic substitution 137 Pd-trimethylenemethane (TMM) 301 – sulfone-substituted 301 o (S)-pentafluoro-g-caprolactone 70 Oppolzer’s camphor sultam auxiliary phaclofen 94 201 phase transfer catalyst 304, 314f. orbital 323 phenyl benzyl sulfoxide 352 organoaluminium reagent 125 –pKa value 352 organoborane 203 phenyl tert-butyl sulfoxide 6 organocatalysis 285, 288, 295 phenyl sulfone 293 organocatalyst 285, 288, 295, 297 – a,b-unsaturated 293 – bifunctional thiourea-tertiary amine 4-phenyl-1,5-diazacyclooctan-2-one 94 297 trans-2-phenylcyclohexanol 49 organometallic reagent 49ff., 89, 125f. (þ)-(R)-phenylethanol 215 organozinc reagent 225 phenyloxirane 180 organozincate 84 N-phosphinooxaziridine 23 oxabicyclo[3.2.1]octane 122 a-phosphorylvinyl sulfoxide 90 oxacycle 216 (2S,3S,4R)-phytosphingosine 164 oxathiazolidine oxide 9f., 25, 233ff., 238f., Pictet-Spengler reaction 82 260 piperidine 86, 134, 188, 280 – N-activated 235 PM3 calculation 401 – endo/exo selectivity 238 polarizability 163 – precursor 239 polarized continuum model (PCM) 403f. 1,2,3-oxathiazolidine-2-oxide 9f., 25, 234, polymeric chiral metalloporphyrin 261 complex 20 oxathiazolidine-S-oxide 233 polyoxamic acid lactone 258f. oxaziridine 22ff. pre-catalyst 200 oxazolidinone 12, 308 l-proline 169f. oxazoline 74, 78, 167, 271f., 386f. a-propanoate equivalent 365 – chiral (bis) 167f., 387 propargyl carbinol 59 oxidant 24 prostaglandine intermediate 358 oxidation 2, 12, 14, 22, 171ff., 237 pseudopteroxazole 222ff. – catalytic 12 Pummerer intermediate 78 – sulfide 173f. Pummerer reaction 57, 63, 136ff., 139f. oxirane 75f., 91, 179, 183, 186f., 189, 365 – additive 137f., 142 – spirocyclic bis-sulfinyl 91 – chiral center 138f. a-oxoester 167 – interrupted 137, 140 oxosulfonium salt 136f. – mechanism 140f. a-oxy carbanion 323, 329f., 334f., 341, – non-oxidative (NOPR) 69, 140, 369 343 – non-oxidative, mechanism 140 donor 22 – normal 136f. oxygen transfer mechanism 406f. – stereoselectivity 138 – vinylogous 137f., 141 Pummerer rearrangement 69, 76, 136, 141f. Index 427 pyrazoline 120f. remote sulfinyl group 127 130, 412f. – stereocontrol 127 – ortho-directed metallation 130 remote sulfoxide 123ff. 2-pyridyl group 294 d-p p-resonance 163 2-pyridyl sulfone 295, 298, 315 restricted Hartree-Fock (RHF) method – b-aryl-b-alkyl 298 401 – b,b-dialkyl-a,b-unsaturated 298 retro-Michael reaction 21 – b-disubstituted a,b-unsaturated 298 rhodium catalyst 267f., 293f. 2-pyridyl vinyl sulfone 293f. rhodium complex 200f., 246f., 270, 311 (2-pyridyl) 298 – cationic disymmetrically P,C-chelated – b,b-disubstituted a,b-unsaturated 295 270 1-(4-pyridyl)-1-p-tolylsulfinyl ethylene 84 ring-opening reaction 50f., 68, 76, 78, 163, a-pyridylsulfenyl carbanion complex 337 189 – geometry optimization 337 – nucleophilic 76, 78 pyronesulfinylalkene 122 – oxirane ring 76, 78 pyrrolidine 134, 188, 300 – thiane ring 68 – 2,5-disubstituted 300 rotational barrier 325, 352, 377, 388 – endo-pyrrolidine cycloadduct 300 rubiginone A2 106f., 125 pyrroloazepine 113 – retrosynthesis 107 rubiginone C2 106f., 125 q – retrosynthesis 107 quantum mechanical (QM) calculation ruthenium catalyst 267f., 281f., 305 400 Rydberg orbital 401 quenching 380, 383f. – kinetic 393 s quinine 6f. SaN bond 237ff. quinolyl sulfide 338 SaO bond 237f. quinone 106 Salen ligand 16 Salen manganese(III) complex 17 r SC-53116 256f. racemization 323ff., 379 – synthesis 256f. – activation parameters 379 Schiff base 18f. – barrier 324f., 379 – tridentate ligand 18 – kinetics 379 sedridine 112 – polarimetric determination 379 l-Selectride 81, 86, 124, 128 – pseudo first order 379 N-SES aziridine 192 – rate-determining step 324 seudenol 72 radical 95f., 283f., 298f. Sharpless epoxidation 172 -structure calculation 299 shikimic acid 99 radical addition 298 SIAM (bis(sulfinyl)imidoamidine) ligand radical allylation 283f. 252ff. – mechanism 284 sibutramine 259f. – /hydroxysulfoxide 284 – synthesis 259f. rate-determining step 186 [2,3]-sigmatropic rearrangement 108, 110, (R)-recifeiolide 59f. 179f., 196, 199ff., 203 recyclability 222, 307 – catalytic 200 reducing agent 124, 248f. – mechanism 199ff. reduction 56ff., 59ff., 62ff., 65ff., 71, 79, – sulfonium ylide-mediated 199 124f., 128f., 228, 248f., 260, 305ff., 308 a-silyl-a-sulfenyl carbanion 324, 342 – oxaborolidine-catalyzed 307 b-silyl-a-sulfinyl carbanion 354, 358, 363 – transition metal-catalyzed 228 a-silylamine 247f. reductive alkylation 226 – silyl anion addition 248 Reformatzky reagent 12 Simmons-Smith reaction 184 Reissert reaction 280 – sulfonium ylide-mediated 179 remote stereocontrol 123, 126f. solvent influence 76, 333 428 Index

Sonogashira coupling 222 – synthetic utility 321f. spiroacetal 170 – tricarbonyl(h6-arene)chromium complex spiroketal 110 bearing 341 spirolic derivative 142 sulfinamide 9ff., 12, 233ff., 241, 252, spongistatin 176 255f., 260f. stabilized ylide 1921f. – aliphatic 260 – mechanism 192 – application 233ff., 241, 256 p,p-stacking interaction 135 – aromatic 260 stanna-Pummerer rearrangement product – background 234f. 141 – biologically active molecule 256 statine 370 – enantiopure 240 steric approach control 98, 112 – endo/exo selectivity 238 steric effect 135 – ether-functionalized 240 stilbene oxide 180, 183ff., 188f. – Grignard addition 261 – synthesis 183 – ligand 252, 254 b-stiryl p-tolyl sulfoxide 85 – modular asymmetric synthesis 240 Strecker reaction 259 – precursor 235 – sulfinyl imine-based 259 – sulfinyl auxiliary 241 substitution 330f. – synthesis 233ff., 236ff., 240 sugar alcohol 45f., 48 – transformation into enantiopure sugar sulfinate 6 sulfoxide 9 – diastereoselective formation 6 – tunable chiral 261 sulfenate ester 33 b-sulfinamine 369 – oxidation 33 sulfinate 3ff., 6ff., 10, 36ff., 49f. sulfenic ester 52 – Andersen method 3f. a-sulfenyl carbanion 321ff. – diastereoselective formation 5ff., 49f. – configurational stability 323ff., 326 – precursor 8 – diastereoselective reaction 326ff. – synthesis 4, 33 – enantioselective reaction 329, 332ff. – synthesis using alkaloid 7 – 1,2-induction 326f. – synthesis using 2-phenylcyclohexanol 5 – preparation 322f. – synthesis using sulfite 7ff. – properties 321f. sulfinate ester 48 – racemization mechanism 323ff. – C2-symmetric bis- 48 – secondary 327 sulfinate ketimine 260 – stabilization 322f. – reduction 260 – a-stannyl allyl sulfide-derived 328 sulfinated electrophile 123ff. – tertiary 328f., 340 sulfinated nucleophile 130 sulfenyl group 321ff. sulfinic acid ester, see sulfinic ester – properties 321f. sulfinic ester 31ff., 39f., 42, 52 a-sulfenyl-b-ketosulfoxide 67 – asymmetric oxidation 32 sulfenylation 73 – catalytic 35 sulfenylketosulfoxide 67 – chiral ester functionality 40 – reduction 67 – diastereomeric 31, 40ff. sulfide 12, 14, 22, 182ff., 185ff., 191, – enantiomeric 31ff. 321f., 324 – structure 31 – C2 symmetric 183, 186 – synthesis 32ff., 40 – catalytic use 188f. – synthesis using optically active tertiary – a-chirality 322 amine 33, 35 – CMO-catalyzed oxidation 173f. – synthesis using sulfinyl chloride with – formation 183 achiral alcohol 33ff. – a,b-functionalized 137 – synthetic method 32 – a-lithiated 324, 326f., 336ff., 342 – a,b-unsaturated 44 – oxidation 12, 14, 22 sulfinimine 241 – structure 183 – synthesis via condensation 241 Index 429 a-sulfinyl acetate 364f. – stereoselective SN2 displacement 140 – masked 365 – stereoselectivity control 71f., 111, 119, (Z)-sulfinyl acrylonitrile 103 123, 130, 132 a-sulfinyl aldehyde 77 sulfinyl imine 236, 241f., 244, 246f., 250, N-sulfinyl a-amino 1,3-dithioketal 246 254, 256, 259 N-sulfinyl a-amino ketone 246 – ligand 254 ortho-sulfinyl benzylcarbanion 135 a-sulfinyl imine 80 a-sulfinyl carbanion 351ff., 354ff., 357ff., – cyclic 80 360f. N-sulfinyl imine 165, 241ff., 244 – alkylation 354ff. 1,3-sulfinyl induction 75 – carbonyl addition 360 4-sulfinyl isoxazole 117 – configuration 352, 395 sulfinyl ketimine 248f., 257 – conformation 352 – reduction 248f. – conjugated addition 357ff. sulfinyl quinone 105f. – geometry 352 2-sulfinyl quinone 105 – imine addition 367ff. sulfinyl sulfur 56 – lithium salt 352 sulfinyl transfer agent 234f., 237 – properties 351f. – cyclic 237 – stereochemistry 351ff., 360 N-sulfinyl-a-amino-1,3-dithiane 166 – stereogenic center formation 361f. sulfinyl-directed [5C þ 2C] intramolecular a-sulfinyl carbon 362f. cycloaddition 402 sulfinyl chloride 33ff., 37f., 41f., 44, – reaction path 402 46ff., 49, 411 bis(sulfinyl)imidoamidine (SIAM) ligand – rapid racemization 35 252ff. – a,b-unsaturated 44 a-sulfinyl-a,b-unsaturated ester 88 sulfinyl cyanohydrin 78 – nucleophile approach 88 a-sulfinyl cycloalkanone 77 sulfinylation 6, 37f. sulfinyl diazine 130 – catalytic 37 – ortho-directed metallation 130 sulfinylbenzylcarbanion 132ff. sulfinyl diene 107ff. b-sulfinylethylamine 367 – p-facial selectivity 108 1-sulfinylethylene 83 – reactivity 108 sulfinylimine 234ff., 240 – 1-sulfinyl diene 107f., 110 – background 234 – 2-sulfinyl diene 108ff. – synthesis 234ff., 240 sulfinyl dienophile 96ff. a-sulfinylketimine 82f. – cyclic 100 N-sulfinylketimine 134 – geminal 99 sulfite 7ff., 38f., 50f. sulfinyl enamine 79 –C2-symmetric transformation 8 – endocyclic 79 – cyclic 50f. – reduction 79 – cyclic, derived from C2-symmetric sulfinyl epoxide 59, 74, 353 alcohol 8 (E)-a-sulfinyl ester 363 – dissymmetrical 7 sulfinyl ethylene 97, 111, 121 – prochiral 38 – dipolarophile 111 – ring-opening reaction 51 – reactivity 111 sulfonamide 307f. sulfinyl furanone 114 – polymer-supported 307f. sulfinyl group 55ff., 107, 111, 118f., 123, ion 21 128, 130, 132, 140, 236, 288 – catalytic arylation 21 – a-C 57 sulfondiimide 209 – chiral auxiliary 57 sulfone 291ff., 293, 300, 302, 304ff., 307ff., – electron-withdrawing 236 314ff., 380ff., 383ff., 386ff., 389f., 392ff., – p-facial selectivity control 119 395 – nucleophilic substitution 137 – alkylation 390, 392 – regioselectivity control 118 – a-amido 314 430 Index

sulfone (cont.) – dialkylamino-substituted 389f. – base-mediated H/D exchange experiment – dynamic kinetic resolution 396 382 – enantiomerization 377f. –(R,R)-configured 388f. – external trapping 383 –(R,S)-configured 389 – hydroxyalkylation 382 – deprotonation 381f., 384f., 389, 392ff., – in-situ trapping 383f. 395 – lithium salt 375f. – deuteration 382 – oxazolidine-substituted 391 – enantiomerization 385 – protonation 381, 383 – epoxidation 304 – reaction 392 – a,b-epoxy 304 – stabilization mechanism 377 – b,g-epoxy 304 – stereogenic center addition 388ff., 391 – formation 385f., 389 – structure 375f., 389f., 395 – a-functionalized 314f. – synthesis 392 – heteroaryl 292f. a-sulfonyl carbanion salt 376, 389f., 393ff. – g-hydroxy-a,b-unsaturated 306 – monomeric 394 – hydroxyalkylation 388 – racemization 379 – g-keto-a,b-unsaturated 306f. – structure 376, 389f., 394f. – metal-coordinating 315 sulfonyl chloride 43 – prochiral 384ff. sulfonyl cyclopropane 313 – reduction 306f. sulfonyl group 292ff., 298, 394 – silylated 384 – heteroaryl 292f., 298 – substituted 314f. – metal-coordinating 291f., 298, 315 – a,b-unsaturated 292f., 300, 302 – rotation 394 – b,g-unsaturated 302 N-sulfonyl imine 371 sulfonimidamide 209 a-sulfonyl radical 299 sulfonium salt 137, 181ff., 187, 190, sulfonyl trimethylenemethane synthon 301 195ff., 198f. N-sulfonyloxaziridine 23 – aziridination 190 3-sulfonylpyrrolidine 300 – camphor-derived 190 sulfoxidation 13f., 16, 23, 172, 405ff., 408ff. – deprotonation 181 – Al-catalyzed 21 – formation 182 – B3LYP calculation 406 sulfonium ylide 179ff., 187, 191, 194, – 1,2-bis(tert-butyl) disulfide 406f. 197, 203, 404 – iron-catalyzed 20 – conformation 191 – manganese-catalyzed 17 – preparation method 180ff. – mechanism 406, 409f. – reaction 179ff. – steric model 408 – stereocontrol conditions 182 – Ti(Salen)-catalyzed 16 – stereogenic element introduction 182 – using Ti/binaphthol complex 15 – sub-stoichiometric formation 197 – using Ti/1,2-diol complex 14 – theoretical investigation 182 – vanadium-catalyzed 18, 406ff., 409 a-sulfonyl carbanion 291, 315, 375ff., sulfoxide 1ff., 6, 9ff., 13f., 55ff., 123, 172, 378ff., 381ff., 384ff., 387ff., 390f. 234f., 237f., 265ff., 268ff., 274ff., 279, 281, – alkylamino-substituted 390 283, 285ff., 288, 353f., 400, 403, 405, 409, – alkylation 392 414 – allylation 381f. – application 281, 283f. – aryl-alkyl-substituted 375 – bonding mode 267 – asymmetric reaction conditions 380 – C2-symmetric bis- 274, 283, 366 – chirality 375, 382f. – coordinating transition metal 414 – configurational labile 382ff., 388 – coordination mode 266f. – configurational stability 378ff., 388 – cyclic equatorial 354 –(R,M)-configured 395 – ligand 265ff., 274, 283f., 287f. –(S,P)-configured 395 – lithiated 353f. – conformation 375, 389 – main synthetic routes 2 Index 431

– neutral coordinate-organocatalyst 284 t – non-enzymatic asymmetric tandem reaction 91ff. synthesis 2ff. – intramolecular Michael addition/enolate – stereoselectivity control 123 alkylation 359 – structure-activity study 286 – involving Michael-type addition 91, 93 – switching to sulfoximine 403 tartaric acid diester 12f. – synthesis 1ff., 9f., 238 tertiary amine 33, 35 – synthesis using Evans auxiliary 11 tetrahydrofuran 66, 69, 95, 163, 216f. – synthesis using 1,2,3-oxathiazolidine- – bicyclic 220 2-oxide 9f. – derivative 216, 220 – synthesis using prochiral sulfide 405 – trans-2,5-disubstituted 167 – synthesis using racemic precursor – formation 95 409ff. – substituted 217 sulfoxide-metal complex 267 – 2,3,5-trisubstituted 163 sulfoximine 209ff., 212ff., 224, 227 tetrahydroisoquinoline 371 – application 209ff., 213 tetrahydropalmatine 368 – biological activity 210 tetrahydropyran 66 – C2-symmetric bis- 212, 226 tetrahydropyrrole 117 – chiral auxiliary 214 tetralone 361 – chiral ligand 224 thermodynamic conditions 113f. – enzyme inhibition 210 thermodynamic control 368f. – general preparation process 211 [2,3]-thia-Wittig rearrangement 328 – herbicidal activity 210 a-thio carbanion 326, 334, 340f. – insecticidal activity 210 thioacetalization 162 – lithiated N-methyl 215 thioanisole lithiation 322 – N,N-type 227 thiocarbamate 321, 326, 334, 339ff. – N,O-chelating 227 – lithiated 341 – P,N-type 227f. thiolane 189 – structural modification 211ff. Ti/binaphthol complex 15 – structure 209ff. Ti/DET complex 12f. – N-substituted 212 Ti/DET methodology 13 – synthesis 209ff., 212f. – industrial application 13 sulfoxonium ylide 194 Ti(Salen) catalyst 16 sulfur center 403ff. Ti/triethanolamine complex 15 – directing effect 403 titanating agent 219f. sulfur derivative, a-substituted 136f. titanation 219f. sulfur function 55, 400 titanium complex 12ff., 15, 308f. – directing effect 400, 403 titanium TADDOL complex 308f. – stabilizing mechanism 163 TMPOO (N-toluenesulfonyl-4-methyl-5- sulfur precursor 3ff. phenyl-1,2,3-oxathiazolidine-2-oxide) 239 – use 3ff. – S-N bond 239 sulfur ylide 93f., 179ff., 182, 400, 403f. p-toluenesulfinamide (p-TSA) 235ff., 240 – application 179ff. – synthesis 236f. – conformation 182 p-toluenesulfinate 46ff., 237 – epoxidation 405 – cellulose-derived 47 – reactivity 403f. – b-cyclodextrin-derived 47 – stereocontrol conditions 182 p-toluenesulfinic acid 41 – theoretical investigation 182 – condensation with menthol 41f. – structure 404 p-toluenesulfinimine 235f. – synthesis 179ff. – synthesis 236 sulindac ester 14 p-toluenesulfinyl chloride 41 (–)-swainsonine 302 p-toluenesulfinyl imine 259 swinholide 176 N-toluenesulfonyl-4-methyl-5-phenyl-1,2,3- (–)-sydowic acid 71 oxathiazolidine-2-oxide, see TMPOO 432 Index

p-tolyl group 236 – b-substituted 300 p-tolyl methyl sulfoxide 19, 367 vinyl sulfoxide 83ff., 86, 88, 91, 95, 97f., p-tolyl sulfoxide 3, 361 107, 109, 111f., 115f., 121ff., 137, 220, (R)-a-(p-tolylsulfinyl) ketoxime 81 356f., 363, 401 – reduction using l-Selectride 81 – ADC substrate 111 (R)-a-(p-tolylsulfinyl)acetophenone 70 – b-alkoxy 95 p-tolylsulfoxide 371 – alkylation 356f. N-tosylnorephedrine 11 – conformation 401 total synthesis 222, 257 – dienophilic feature 97 –(6R,7S)-7-amino-7,8-dihydro-a-bisabolene – electron-withdrawing group influencing 257 reactivity and stereoselectivity 88, 97 transfer hydrogenation 268ff. – functionalized 221 – Ir-catalyzed 269f. – gem-disubstituted 99f. – Rh-catalyzed 268 – lithiated 357, 363 transformation 55 – reactivity 97, 100 – sulfinyl group-mediated 55ff. – selectivity 97 transient chiral metal-complexed , – stable conformer 401 selective transfer 199 – 1-substituted 88ff. transition state 278f., 334, 362, 368, 402f., – 2-substituted 84 412f. – trans-substituted 98, 100 – calculation 403, 412f. vinyl thioether 137 – pro-R 408f., 412f. – g-substituted 137 – pro-S 408f., 412f. vinyl p-tolyl sulfoxide 101 transoid 191f. –(Z)-substituted 101 tricycle[4.3.0.0]nonenone 312 vitamin E intermediate synthesis 363f. tricyclic compound 312f. triisopropylphenylsulfinamide (TIPP w sulfinamide) 248 Wittig reaction 223, 328 trimethylsilylcyanide (TMSCN) 82 TS-cisoid addition 192 y TS-transoid addition 192 ylide 181, 197f., 200, 203, 403f. tungsten catalyst 20 – amide-stabilized 404 – chirality transfer 200 u – conformation 203 umpolung synthon 161f., 177 – ester-stabilized 197 hydrogen peroxide adduct (UHP) 16 – facial selectivity 182, 198 – formation 181f., 197, 199f. v – mechanistic model 197 vanadium catalyst 18, 406ff. – metal-associated 200 – diastereomeric forms 407f. – precursor 192, 194, 196, 198 – Schiff base-derived 18 – prochiral 182 vinyl aziridine 194, 251 – semi-stabilized 404 vinyl cyclopropane 196, 198 – structure influence 200 vinyl epoxide 186 vinyl ether 309f. z vinyl sulfinyl allene 108 Zimmerman-Traxler chair-like transition vinyl sulfone 292ff., 296ff., 300f., 315 state 362, 368 – conjugate addition 294 zinc alkoxide 225 – rhodium-catalyzed cine-substitution 293 zinc complex 299, 361f.