Key to abbreviations for chiral auxiliaries

This is a list of chiral auxiliaries, mostly chiral ligands, which have beendiscussed in this book or have closely related structures . They are oftenreferred to by acronyms, so their structures are given here. This is notintended to be a comprehensive glossary of acronyms, but serves as a guideto material presented in the book.

ALAPHOS

APPM

YPPhZ

Meyo

PPhz

BCCP (page 168)

BCPP

BDPP(pages 147, 153, 154, 175, 176)

)-PPhZ

s.,""

BINAP(pages 147-150, 153-155,157-161,164,166-174,176,196-198,279-285,287 ,289 ,291 ,293,297)

BCPM (pages 168, 169)

PPhz

PPhz

KEY TO ABBREVIATIONS FOR CHIRAL AUXILIARIES 407

BINAPHOS (page 219)

BINOL (pages 16, 17, 18,44, 133, 141,248,252, 388)

OH

OH

BITAP (page 173)o-BITAP

m-BITAP

BPPFA (pages 147, 153, 154)BIPHEMP(pages 147,149,150,154,158,159,162,168,170,171,172)

Me

Me

Bipymox-ip (page 214)

PPh2

PPh2

H Me

~NMe2~PPh2

Fe

@tPPh,BPPFOH (pages 47,164,165,284)

408 ADVA NC ED ASYMMETRIC SYNT HESIS

BPPM (pages 147, 149, 159, 167- 169)

PPhz

_O"'O)(yPPhz

BuTRAP (page 214)

BZPPM

CAPP (pages 147,1 57,1 59)Pheny1-CAPP

PPh zPhNH)((PPhz

CBD (pages 147, 149, 157, 159, 163, 174)

CIDRAPHOS (pages 147, 149, 154, 155,157,163,173,174,219,309)

CYCPHOS (pages 175, 176)

DAG (pages 35, 40, 241,242, 244, 248)

DAIB (pages 11, 13)

~ N~a-J:oHDBP-DIOP (page 219)

DEGUPHOS (pages 147,149,155)

KEY TO ABBREVIATIONS FOR CHIRAL AUXILIARIES 409

DET (pages 9,10,16,367,370)

Et02CxOH\\

Et02C OH

DHQ (pages 379, 381)

DHQD (pages 379, 381)

(DHQDhPHAL (pages 381, 382,384-386)

N-N

(DHQD)-0--\d-0-(DHQD)

U(DHQDhPYR (pages 381,382,386)

Ph

(DHQD)-O~O-(DHQD)

N'tN

OMe

DHQ-IND (pages 382, 384)

o(DHQ) -O~

W(DHQhPHAL (pages 381,382)

DHQD-CLB (page 384)

°(DHQ)-Oh

QCI

DHQD-IND (pages 382, 384, 386)

°(DHQD) - 04'

W

N-N

CDHQ)-0--\d-0-CDHQ)

U(DHQhPYR (pages 381,382)

Ph

(DHQ)-O~O-(DHQ)

NyNPh

410 ADVANCED ASYMMETRIC SYNTHESIS

mop (pages 146, 147, 149, 153, 154,157,158,160,165,173,174,195-197,215,216,219)

mop'

DIPAMP(pages 147-149,153,154,157,168,169,173,174)

OMc

Ph ~I"",,'V

( OMe

P~hV

DIPT (pages 67, 371)

i-pr02C

XoH

",

i-Pr02C OH

DUPHOS(pages 147, 149, 153, 175)

EapBH2(pages 187, 188)

Et

~f·H'

Et-DUPHOS (pages 154, 175, 176)

FPPM

Icr2BH (pages 184, 188)2.dlcr2BH

HB2 (" ",A)

MeYMe

KEY TO ABBREVIATIONS FOR CHIRAL AUXILIARIES 411

IpczBH (pages 183,184,188)

IpcBHz (pages 187, 189, 191,205)

Me

~\B"2~\\

LEUPHOS (page 295)t-LEUPHOS

H, (PPh2

t Bu'j--.. NMe2

Lgf:zBH (pages 188, 189)

Me Me

HB(~)I 2

Me

MCCPM (page 165)

MDBHz (pages 187,188)

Me-DUPHOS (pages 168, 170)

MellllQ

Ct ~:~J:5

MeO-BIPHEP(pages 147,149,150,159,160,162,166-168,170,173)

LinUBH(pagesl84, 185, 188)

Me

H~..... B

I II"

Me

MeO

Mea

PPh2

PPh2

MOD-DIOP (pages 147, 159)MAPP (page 19)

Ph 0Me<,N~N

I

"

HX°-y-PAr:z

O~PAr2

"

Me

h-qOM'

412 ADVANCED ASYMMETRIC SYNTHESIS

MOP (pages 215-217) PHEGLYPHOS

OMe

PPh 2

MSCPM

PCY2M,SO,_t!.PPh2

NORPHOS(pages 147, 149, 154, 173)

~PPh2

\\

IPPh 2

PapBH2 (pages 187,188,190)

Ph

~rBH'

PCPM

(PhhCDHQhPHAL (page 381)

N-N(DHQ)-OWO-(DHQ)

~~,Ph Ph

H~PPh'

Ph' NMe2

PHEPHOS

H" (PPh2

PhPNMe2

Ph-TRAP

Me

PNNP (pages 147, 156)

Ph--lN~~PhI I

Ph 2P PPh 2

PPFA (pages 292, 293, 295, 298)

PRONOP(pages 167, 168)

O~OPCP2IPCP2

KEY TO ABBREVIATIONS FOR CHI RAL AUXILIARIES 413

PROPHOS (pages 147,149, 153,1 54)

Me

1P P h2

PP h2

Pybox-ip (page 214)

Pymox-tb (page 214)

Pythia (page 214)

rI1H'N~S

N HN~C0 2Et

RAMP

cx..--OMe

N HINH2

SAMP (page 340)

~OMeINH2

TADDOL (pages 214, 247)

tNap Nap

o = 0>< - 'p-Nap

o dNap Nap

VALPHOS (page 288)

:/

" " PP h2

NMe2Me

Me

Index

ab initio calculations 201acetophenone 213acetylalanine 152acetylphenylalanine 152Achiwa 157, 166acrylimide 134acyl boronates 139acyl complexes 49acylases 262acyloin condensations 271AD-mix 384

IX 378,380P 378,380

adrenergic blocking agent 163adrenoceptor agonist 164aggregation 114,118,119agrochemicals 7Akermark 307aklavinone 362Alcalase 262alcohol dehydrogenase 265,266aldol reaction 4,9,27,239,344

aza- 33homo- 243nitro- 22

aldolase 271,272alkene epoxidation 15allose 233allothreonine 173allylic acetates 301allylic alcohols 159,166,367,368,369allyltitanation 245aluminium 135,136Amano P-30 lipase 269amino acid dehydrogenase 265, 267amino acids 7,23,49,53,101 ,128,132,

135,141,152,172,204,241,242,263,267,330,349,355,388«-alkyl 368p-hydroxy-IX- 369

amino alcohols 9,11 ,12,19,34,101 ,226,229,253 ,254

aminocarbene 355amphetamine 8amphotericin B 76analytical methods

CD 61GC 245HPLC 95

molecular weight measurements 18~~Ft 14,66,76,95,115,157,188,233,

237,238,244,245,248,299,321OFtD 61X-ray structure determination 13,61,

105,106,119,128,136,247,233,234,236,238,299,306,307,308,379

Andersen 61Andrus 388A~IC S.P.A. 156Annunziata 64anomeric effect 84, 131anti-selectivity 37,203 ,204,241 ,247,250anti-substitution patterns 316antiperiplanar 201antisense oligonucleotides 249arabino-configuration 249arabinose 130,251aroylhydrazones 175arylketimine 175aspartam 7,153,263Aspergillus acylase 262Aspergillus niger 264, 265, 267asymmetric

amplification 4,9conjugate addition 19deprotonation 111-125dihydroxylation 379,383epoxidation 4,9,231 ,343 ,356,368,395hydroboration 181-211,404hydrocyanation 23hydroformylation 217hydrogenation 146-180hydrosilylation 212induction, definition of 2oxidation 9,367-394

of thioethers 387reduction 21,146-180,265synthesis

design of 1-6generations

first 3, 240, 401fourth 3, 297second 3,240,401third 3, 242, 397

importance of 7-8transfer of tricarbonyliron 328transformation 123,295

ate-complexes 190,251,252

416

auxiliar y ligands 318axial chirality 279aza-aldol 33azanorbornene 289

Backvall 388Baeyer- Villiger oxidation 268, 269bakers' yeast 265-268Balenovic 609-BBN 204,205BCCP 168BCPM 168, 169bda 292BDPP 147,153,154,175 ,176BDPP (sulfonated) 175, 176BDPPH 176BDPPM 157Beauvaria sulfurescens 264, 265, 270Beck 155benzoquinolizine 104benzoylhydrazines 175bidentate phosphines 40, 146-151,

153-177,196-198,214,218-220,278,279,281-293,295-297,305,306,310

BINi\P 147-150,153-155,157-161,164,166-174,176,196-198, 279-285,287,289,291,293 ,297

BINi\PHOS 219binaphthol 16,17 ,18 ,44,133 ,141 ,248 ,252,386

binaphthols 138binaphthyl 279BINOL 16,17,18,44,133,141,248,252,386

biological activity 6biotechnology 260-274,398-399biotoxication 8BIPHEMP 147,149 ,150,154,158 ,159 ,

162,16 8,170 ,171 ,172biphenanthrol 133biphenomicine i\ 173Bipymox-ip 214bis(dimethylamino)naphthalene 286,288bis(diphenylphosphino)pyrrolidine 163bis(methoxymethoxymethyl)pyrrolid ine47

bisoxazoline 388bisphenylethylamide 112,119BITi\P 173P-blocker 8boat transition state 241Bolm 20borane

-dimethylsulfide 183-THF 42

borinic esters 190, 207bornane-I 0, 2-sultams 29,3 1,48, 54borneol 229

INDEX

bornyl-IO,2-sultam 49borolanes 192, 193boron 27,38,1 36boronic esters 190,209Bosnich 309BPPFi\ 147,153 ,1 54BPPFOH 147,164,165 ,284BPPM 147, 149, 157, 167-169BPPP 164brasilenol 115Brassard 's diene 137, 140Braun 32,33brevicomin 99,100Brown 156Brunner 288Buchwald 177bulgecenine 356Burk 147,153,175butadiene 131,132butene 188,189,219butenolides 68BuTRi\P 2144-butylcyclohexanone 112t-butyldimethyl silyl triflate 31t-butyl hydroperoxide 373

C. militaris 388c, axes 392c, symmetric 13,34 ,47 ,79 ,85 ,93 ,94 ,112 ,

133,136,142,147 ,151 ,153,164,173 ,193 ,238,279

Cahn-Ingold-Prelog nomenclature forsulfoxides 61

calamenene 352calculations

ab init io 20Iforce field 237MM2 299,379semiempirical 190

calyculin i\ 29camphor 113camphorate salts 387camphorsulfonyl imines 140Candida cylindracea 261, 262cannabisativine 140capnellenol 290Ci\PP 147,157,159carbacyclin 116,398carbapenem 173carbidopa 155carbocyclic nucleosides 263carbohydrates 130carbomycin B 323, 324, 336carbonyl insertion 321, 322carbo vir 263carboxypeptidase 262carene 184,186carnitine 267

INDEX 417

Carpenter bee pheromone 383Carre ira 44castanospermine 284catecholborane 196-198,203,204CBD 147,149,157,159,163,174central nervous system (CNS) 8chair transition state 35,241,243,246chalcone 226chelation control 97, 109chiral auxiliary, definition 3chiral enolate equivalent 400chiralpool 2,126 ,147chiral reagents

allylborane nucleophiles 341aminals 93-110bases 339boron enolates 341cobalt clusters 341dienes 131,140dienophiles 126,137,139,141enolates 27-59enones 328nucleophiles 293,303 ,326,336,341phosphines 40,146-151 ,153-177,

196-198,214-220,281-293,295-297 ,305-309

sulfoxides 60-92,123,128,131,386,388chiral shift reagents 322, 339chirality

axial 279memoryof 53planar 318, 338, 349relay 2,3 ,303,369

CHIRAPHOS 147,149,154,155 ,157,163,173,174,219,309

Chirasil-Val 245chloramphenicol 383chromium 108,293,298,352Chromobacterium viscosum 262chymotrypsin 262cinchonide 52Cinquini 64citroneIlol 161cladospolide A 78, 83Claisen 401closed n-systems 317cobalt 150,161 ,218cod 148,149,151,175,176,201,215,216cofactor-recycling 265conduritol C 269conjugate addition 96, 103, 222-230 , 344,

352,400contraceptive activity 7control

by convex asymmetry 248chelation 97, 109kinetic 108,121,304,338lateral 320

reagent 3, 182stereoelectronic IIIsteric 109substrate 2, 3, 182, 200thermodynamic 76,105,108,121,237,244

copper 19,73,75 ,96,97,99,103-105,109,224-228,336,344

Corey 32,34,38,44,64,135,136Cotton effect 61Cr(CO)6 108Crabtree 200Cram's rule 246cross-coupling 275,29218-cro~-6 52,350cryptone 115Cunninghamella elegans 388cuprates

higher-order 227medium-order 227

Curvulariafalcata DAH 268CY2BH 202,205cyanocuprates 73,76cyanohydrin 16,23 ,270cyclobutadiene 317cycloheptatriene 338cycloheptenone 19,224,227cyclohexadiene 141cyclohexadienediols 269cyclohexene 388cyclohexenones 224, 360cyclopentadecenone 226cyclopentadiene 127-130,133-137 ,139cyclopentadienone 356cyclopentadienylligands 49,233,321 ,323,

326,343,344cyclopentadienylmolybdenum 344cyclopentene 387cyclopentenone 227cyclooctadiene 148,149,151 ,175 ,176,201,215,216

CYCPHOS 176, 175

d1nucleophiles 239,251d3-nucleophiles 239DAG 35,40,241 ,242,244,248DAIB 11,13Danishefsky 137,138Danishefsky 's diene 131, 141Davies 50, 55Davies / Liebeskind enolate equivalent 49,50,55

Davis oxaziridine reagents 53DBP-DIOP 219de novo asymmetric synthesis 2DEGUPHOS 147,149,155Degussa 267Degussa Co. 155

418

dehydroalanine 153dehydroaminoacids 153,155,157dehydroerythronolide A seco acid 371dehydrohalogenation 123dehydropeptides 155dehydrophenylglycine 153deltamethrin 7deoxynojirimycin 2712-deoxy-D-ribose 782-deoxy-L-xylose 78Deprenyl 8Dess-Martin 56desulfonylated 326desulfurization 68,74,79,84,85DET 9, 10,16,367,370deuterium isotope effects 373DHQ 378,380DHQ-IND 382,383DHQD 378,380DHQD-CLB 384DHQD-IND 383,384,386(DHQDhPHAL 380,382,384--385(DHQDhPYR 380,382,385(DHQhPHAL 380,382(DHQhPYR 380, 382I, 2-diamines 931,2-diphosphines 1471,4-diphosphines 1471, 3-dithianes 388diacetone-D-glucose 35,40,241,242,244,248

dialkoxycyclopentadienyltitaniumchlorides 233

dialkylboron enolates 27dialkylzinc reagents 11,13,21,229,253,

254DIBAL 66,73,76,84,88diborane 66dicarbonyl(cyclopentadienyl) iron 321dicarbonyl(cyclopentadienyl)molybdenum323,326,343

Diels-Alder 16,18,22 ,106 ,126-145hetero- 137inverse electron demand in 106

dienophiles 126,128,130,134dienyl alcohols 367diethyltartrate (DET) 9,10, 16,367,370diethylalumin ium chloride 50diethylzinc 9,11,21diHETE 348dihydro-LTB4 348dihydroactinidiolide 115dihydrocitronellol 162dihydrofuran 285,287dihydroquinidine 378dihydroquinine 378dihydroxycalamenone 352dihydroxyserrul atic acid 352

INDEX

diisopinocampheylborane 183,247diisopinylcampheylboron triftate 33diisopropyl tartrate (DIPT) 367,371diketodisulfoxides 85dimeric catalysts 371(2-methoxycarbonyl)cyclopentanone 1732, 3-dimethylbuta-l , 3-diene 135dimethylcyclohexanone 112, 113dimethyl fumarate 135dimethylcuprate reagents 343(2,5-dimethyl)methoxyborolanes 192dimethylzinc 13DIOP 146,147,149,153,154,157,158,

160,165,173,174,195-197,215 ,216 ,219dioxin 280DIPAMP 147-149,153,154,157,168,169,

173,174dipeptides 23,155diphenylsilane 212diphenylzinc 228DIPT 367,371Donaldson 345dopa 155dopamine 389dopamine p-hydroxylase 389,390double asymmetric hydrogenation 159double stereodifferentiation 4,132,139,

162,197,247drug receptor 7drugs 218DSM-ToyoSoda 263DUPHOS 147,149,153 ,175Duthaler 35dynamic kinetic resolution 173dynamic resolutions 262

EapBHz 187, 188Electric eel choilinesterase 262elimination, p- 276,280enamides 157,158enantiocontrol by convexasymmetry 248enantioface differentiation 225, 278, 246,279,298,403

enantiomer recognition 6enantioselective autocatalysis 4, 15,24enantiotopic

alkenes 289,404group differentiation 288,398,400,401leaving groups 309termini in it-ligands 325

enant iotopos 278, 288, 403endo 318

1/1- 318,346,348ene reactions 17,236enediyne natural products 341enzymatic reactions 121

epoxidation 378hydrolysis 260,261

INDEX 419

oxidation 61,268reduction 265

enzymes 260-268, 270-274epimerisation 62, 338epoxides 6,10,75,77,78,95,260,261,264,265,343,347,357 ,368-375,383,386,397,399,400

eptazocine 282, 284EQ 113,117,118erythro 4,42Escherichia coli 272ester hydrolysis 260, 399esterase 260, 261Et-DUPHOS 154,175,176Et2Zn 229Et2Zn 254ethoxycarbonyltetralone 173ethyl citronellate 160ethylp-tolyl sulfoxide 61ethylapopinene 187ethylenic esters 98ethylmagnesium bromide 322Eu(fod)3 137,138Eufhfc), 137Evans 21,27 ,29,31,46,53,88,240exo 37,304,318,352

t/J- 318,346addition 319,326,330-brevicomin 385

external quench (EQ) 113, 117, 118

Faller 248Fe ('1-CsHs) (CO) (PPh3) 49Feringa 21,388ferrocene 283,292,295ferrocenylphosphines 39first-generation asymmetric synthesis 3,240,404

Fischer carbenes 355FK-506 171,336,370force fieldcalculation 237formate dehydrogenase 267fourth-generation asymmetric synthesis 3,297

formylpyridine 102frontalin 98,100FruAld 272fructose-I, 6-bisphosphate aldolase 271FucAld 272Fujita 398fungi 265

gabaculine 330GC 245Genet 148Geotrichum candidum 262geraniol 161Gerlach 's method 74

Gilman 61,228gingerol 76Gleave 113glucose 35, 131,233, 241glyceraldehyde 249-251glycine 35,48 , 52, 241glycopeptides 264, 272glycosides 260glyoxal 99,100glyoxylate-ene reaction 17gold 39,40goniofufurone 350Grabowski 52Green 339Grignard reagents 61,62,64,98,99 ,101 ,

192,228 ,244,251-253,298,324,337,338,361,395

hafnium 253,254Hajos-Parrish reaction 9,23,401Halpern 156, 160Hanaoka 349hapticity 314,319 ,340Harpp 62Hayashi 215,285 ,287 ,295 ,298,305,308Heck 275Heck coupling 288,289Hegedus 219Helmchen 47,307HETE 344, 345hetero-Diels-Alder reaction 137heterochiral 13,15,18heterodiene 344hexafluoroacetylacetonate 150higher-order cuprates 227hippeastrine 333Hirama 386Hiroi 303HMG -CoA synthase inhibitor 171HMPA 46,48,114,115,117,122,227 ,228Ho 339Hoffmann-LaRoche 168,404hog-kidney acylase 262homoaldol-synthons 243homoallylic alcohols 367, 368homochiral 11,13,15,18,19,20,23, IIIhomocuprates 226Hoppe 234, 243Horner 146horse-liver alcohol dehydrogenase 266,268

horse-liver esterase 262Houk 201HPLC 95hydrazones 175hydrindans 289hydrobenzoin 135hydroboration 181-211 ,404

420

hydrocyanation 23hydrogen peroxide 375hydrogenolysis 53hydrolase enzymes 261hydroxycyclopentenone 162hydroxyketones 381hydroxylation , cis- 379hydroxyproline 226hydroxypyruvate 271hydroxysteroid dehydrogenase 266,268hydroxyvitamin O2 132

ibuprophen 8, 159Icr2BH 184,188Ikariya 159,171imidazolidine 93, 108imines 175immobilization 163in situ quenching 113,116-118 ,123indene 197indoloquino lizine 104Ingold-Thorpe effect 236insecticides 7inverse electron-demand 106, 132inversion of stereochemistry 30Iiodolactonisation 406iodosylbenzene 375ionic reduction 352Ipc2BH 183,184, 188IpcBH2 187,189,191 ,205iridium 150,161,175,200iron 49,50,55,95,296,305,321-324 ,

327-336 ,345-348,357,358 ,360,361Isicon 155isoborneol 229isoborneol-IO-sulfinylauxiliaries 128isobutyraldehyde 243isocyanate 368isopropylidene glyceraldehyde 139isopropylnoradrenaline 8isotopic labelling 62,373ISQ 113,116-118,123itaconic acid 157,159iterative reaction sequences 321

Jacobsen 374,375,388Jacobsen-Katsuki epoxidation 373James 148,175Jansen 21Johnson 269juglone 130

K20s02(OH)4 378K3Fe(CN)6 378,382,383 ,384Kagan 9,16,60,146,153,388Kanemasa 105Katsuki 373,387Kende 29,43

INDEX

ketopantolactone 168,1693-ketosteroids 120kinetic control 108,121,304,338kinetic resolution 4,50,120,122 ,161,162,

173,260-262,285,286,386dynamic 173

kinetic studies 373Kirby 228Kishi 201Klibanov 263Knochel 255Knolker 356Knowles 146,153Kobayash i 22Koga 112-114,120Kondo 339Kunieda 64

LAC 15lactam, p- 100lactamases 262, 263lactate dehydrogenase 265, 267Lactobacilluskefir AOH 268lanthanide catalysts 21lasiodiplodin 74lateral control 320LOA 114leucine 267leucine dehydrogenase 267leukotriene B4 75,348LEUPHOS 295Lewisacid 31, 33, 34, 38, 42-44, 50, 70, 97,126-130,133-135,137,138,140 ,141 ,231 ,234,236,239,242,243,248,253,254,322,348,351 ,352,359,369

Ley 356Lgf2BF 184Lgf2BH 188,189LiAIH4 66, 67LICA 48LiEt3BH 67ligand accelerated catalysis 15ligand classification

IJI 3541J2 276,314-316,321,340,355,356,3591J3 299-312,314-317,322,324,326,354,

356,3591J4 314-316,323-325,328,354,356,3591J5 315-317,327,335,337,338,358,

360,3611J6 314,315,337,338,358,3611J7 3141J8 314auxiliary 318odd and even 315open and closed 316working 318

LimBCI 185

INDEX 421

LimBH 184,185,188limonene 184,185limonylborane 185linear reaction sequences 321lipases 260,261-264,335lipase M (Mu corja vanicus) 264lipase N (Amano) 264Lipozyme 262Lippard 227Liu 326longifolene 184,186LT~ 346LTB4 348Luche 228Iyxo-configuration 249,250

m-CPBA 56,115,190magnesiocuprate reagent 344Majewski 113maleic anhydride 132malic acid 322malyngolide 98, 100Mander's reagent 116manganese 373, 386mannitol 238,249MAPP 19Marko 164Markovnikov hydroboration 197Masamune 27, 34,42,43, 74masked functionality 332, 354McCague 336MCCPMB 165MDBH 2 187,188Me-DUPHOS 167,168,170Me2CuLi 344mechanism of

cross-coupling 277Heck coupling 276Jacobsen-Katsuki asymmetricepoxidation 375

Sharpless asymmetric epoxidation 372medium-order cuprates 227Meerwein-Ponndorf-Verley reduction 21memory of chirality 53menthol 61,62 ,127menthyl acetate 27menthyl p-toluene sulfinate 61menthyl sulfinate 79MeO-BIPHEP 147,149,150 ,159,160,162,

166-168,170,173MeO-DUPHOS 167Merck 159Merck Frosst 371meso

intermediates 11,13,14,18 ,19,261,288,302,304 ,398

bisepoxide 395complexes 304, 308

diacetate 335metalloprophyrins 377methacrolein 133methamphetamine 8methoxyphenyl acetate 281methylbenzylamine 1412-methyl-2-butene 189l-methylcyclopentene 1893-methyl-3-phenylcyc1obutanone 116methyl lactate 76methyl shikimate 330methyl-p-tolyl sulfoxide 16,73 ,84,85methylcarbapenem 162Meyers 33,50,51,129microbial oxidation 388microbial reduction 339Mikami 17,18Mikolajczyk 60, 62Mislow 61, 147mismatched reaction 247Mitsui 27mixed aggregates 112MM2 calculations 299,379MOD-DIOP 147,159molecular biology 273molecular sieves 17, 18,233,237molecular weight measurements 18molybdenum 377monoalkylboranes 186monoisopinocampheylborane 186monomorine I 117Monsanto 155, 159Montanari 60MoOPH 53MOP 215-217M ortierella isabellina 388Mortreux 168Mu corja vanicus lipase 262,264Mucor javonicus ADH 268Mu cor mieheilipase 261, 262Mukai yama 34, 40, 41,93, 98Mukaiyama reaction 242Murahashi 384Musco 297muscone 19mutarotation 62mycoticin A 392Myers 31myrtanylborane 187myrtenol 188

N-bromosuccinimide 50n-butylboron triflate 28N-tosyl-(S)-tryptophan 135n.O.e. 136NaBH 4 66NAD 265NADH 267

422

NADP 265NADPH 267Nagao 398Nagel 155Nap(Ph)SiH z 216naproxen 159,388nbd 148,198neocarzinostatin 343neooxazo1omycin 29nero1 161neuraminic acid 272, 273Ni(acach 229Nicholas reaction 341nickel 19,20,229,341nicotinamide adenine dinucleotide 265nitrile oxides 106nitrilease 264nitro-aldol reactions 22nitroalkenes 131,132NMR 14,66 ,76,95 ,115 ,157 ,188 ,233 ,237,238 ,244 ,245,248,299,321

NO+ 325,337,338,361non-linear

dependence of ee 9-26temperature dependence 378

nonactic acid 86, 88-90nopol 187noradrenaline 388norbomadiene 148norbomene 195,197 ,288NORPHOS 147,149,154,173Noyori 10-12,148 ,150,159nucleic acids 7nucleoside derivatives 127Nugent 256

O'Donnell 52O-methyljoubertiamine 331O-methylmandeloxy dienes 132octene 378odd and even n-systems 315Oguni 9,16oligonucleotides 249oligopeptides 155oligosaccharide 272open x-systems 316Oppolzer 29,31,32,48,49,54,128,137,

141 ,175ORD 61organolanthonide 198organomagnesium reagents 227organozinc 229,298organozinc reagents 228Osborn 150osmium 378,379osmium tetroxide 348OS04 386over-expression 273

INDEX

Overman 275,281oxazaphospholidines 147oxazolidine 129oxazolidinones 27,31,47,53,54oxazolines 33,39, 136,307oxidation of benzene 269oxidative addition 276, 277, 300oxidative insertion 299oxidoreductase 388oxo process 2175-oxo-ProNOP 169oxygen 372oxynitrilase 270Ozawa 285,287

n-allylpalladium 299palladium 113,115,212,275-312pantolactone 129,168pantothenic acid 168papain 262PapBHz 187,188,190Parkinson's disease 155Paterson 38Pauson-Khand reaction 359Pearson 324,328,356PEG-NADH 267Penicillin spinulosum 377pentamethylpiperidine (PMP) 281pentoses 249peptidases 262peptides 23,241periodinane 56peroxy ligand 373peroxycamphoric acid 374Pfaltz 150,227,305PGIz 398PhzCuLi 326(Phh(DHQhPHAL 381PhzSiHz 213,216pharmaceutical products 6,8,164phase-transfer catalyst 522-phenyl-I-butene 1633-phenyl-I-butene 2953-phenylcyclobutanone 116phenyl glyoxal 98phenylalanine 156phenylapopinene 187phenylbutyraldehyde 246phenylethene 197phenylethylamine 60,112phenylethylmagnesium chloride 295phenylglycine 112-114phenylglyoxylicmethyl ester 166phenylzinc chloride 301Philipps 62phosphoaoxazines 226phyllanthocin 47physostigmine 281, 282

INDEX 423

phytenal 252pinene 183, 187, 184, 186pig-liver esterase 261,262,371,400piperazic acid 54planar chirality 318,338,349planar sterogenic unit 278plane of symmetry 395,397,398 ,399

platinium 60,212 ,219PMP 281PNNP 147,156polymer-bound catalyst 162Porcine pancreas (ppl) 262porcine pancreatic lipase 261potential symmetry planes 315PPFA 292,293,295,298PPTS 84,88Pr(hfch 132Pr-DUPHOS 153,154Prelog's rule 267, 268Prelog-Djerassi lactone 335preparation of aminals 93prochiral

intermediates 403ligands 315nuc1eophiles 310

proline 23,34 ,37,93,112,132,141,387,401

prolinol 31,46, 193, 252PRONOP 167,168propanolol 8PROPHOS 147,149,153 ,154prostaglandins 162,404proteases 262proteins 7pseudo-sugars 128pseudoaxia1 94pseudoephedrine 50pseudoequatorial 94Pseudomonas

diminuta 404fluorescen s 262oleovorans 377putida 269,333sp.ADH 268spp. 262spp.lipase 261

Pummerer rearrangement 75-81, 123Pybox

-ip 214Pymox-tb 214pyrethroids 7, 344pyrone 358pyrrolidines 31,46 , 130pyrrolid inone 322Pythia 214

quinones 135

racemisation 302Raney nickel 53,67 ,68,79,85,88,101,102rat-liver microsomes 265Re-face 46,48 , 54, 130,225, 240, 244,245

reagent-controlled diastereoselectivity 3,182

Red-AI 51reductive elimination 277,297Reformatsky reagent 29resolving agents 94resolution

dynamic 173,262kinetic 4,50,120,122,161,162,173,260-262,285,286 ,386

regiodivergent 121,122retention of configuration 190,301reticuline 385Rh2CI2(cod) 156RhaAld 272Rhizopus arrhizus lipase 262Rhizopusjaponicus lipase 262Rhizopusniveuslipase 262rhodium 148,153-157 ,159,161,163-169,

174,175 ,196,212,218[Rh(COD)Clh 195[Ru(benzene)CI2h 156Rhodoco ccus equi 263Rhodoco ccus spp. 264ribo-configuration 249,250ribonuc1eosides 249ribose 7,249 ,251RNA 7Robinson annulation 9,398Rossiter 19,224routiennocin 356roxaticin 171Ru(cod) (2-methylallylh 148ruthenium 148,153-155 ,157,159-163 ,

166,167,169-171,174-175

o-bond migration 276,278, 279S axes 395, 398Saburi 148,159,171Saccharomyces cerevisiae 266salen 373, 386salt effects 112samarium 21, 175SAMP 340Santi 297scandium 22Schneider 64, 395second-generation asymmetric synthesis 3,240,404

Seebach 254selenium 307semicorrin 151(semicorrinato)cobalt 150

424 INDEX

semiempirical calculation 190serine 247Sharpless 15, 385, 386

asymmetric cis-dihydroxylation 378,381

epoxidation 4,9,343,356,395mnemonic 381

Shibasaki 22,275,281,282shikimic acid 330showdomycin 116,128Si-face 32,39-41 ,46-129,137,244,248,249(SiahBH 206sialic acid aldolase 272, 273(SiamhBH 205SiCl4 134side-on alkene ligands 278, 314silicon 31silylenol ethers 42silyl ketene acetals 42,44sitophilate 322sodium hypochlorite 373Soladie-Cavallo 339sparteine 234, 235spinach 272spiroacetals 84, 85spirocycles 281spirooxindoles 281SpringIer 150stannylenol eters 328stat ine 171stereoelectronic control IIIsteric control 109sterochemistry of /I-elimination 280steroids 200,400Still 205Stille 219,275Stillecoupling 293stoichiometric rr-complexes 313-366strategy oflateral control 320styrenes 218, 378substrate-controlled diastereoselectivity 2,3,182,200

subtilsin 262sugar 131sulcatol 266, 267sulfates 384sulfideoxidations 10, 16sulfides 60sulfinate esters 62sulfinylepoxides 73sulfonamide 379sulfonated diphosphines 163sulfonates 370sulfones 60sulfonimines 175sulfoxides 60, 386, 387

Cahn-Ingold-Prelog nomenclature 61cyclic 122

/I-keto 60-92vinyl 128

sulfoximine 326sulfur 307sultams 29,31,48,128,137,141 ,175Suzuki 275Suzuki coupling 277,292Swem oxidation 79sym-tetraisopinocampheyldiborane 183symmetrical bisalkenes 403symmetry plane 398,399 ,401syn 37

-diastereomers 250-elirnination 201-periplanar 105,280-selectivity 204, 241,250, 292

Syntex 159synthesis gas 218synthesis of

5-HETE 344, 345aspartame 263biphenomicine A 173brasilenol 115brevicomin 99,100bulgecenine 356calamenene 352calyculin A 29capnellenol 290carbacyclin 116,398carbapenem 173carbomycin B 323, 324, 336carbovir 263Carpenter bee pheromone 384castanospermine 284chloramphenicol 384c1adospolide A 78, 83conduritol C 269dehydroerythronolide A seco acid371

deoxynojirimycin 271diHETE 348dihydroxycalamenone 352dihydroxyserrulatic acid 352dopa 155enediyne natural products 341eptazocine 282, 284exo-brevicomin 384frontalin 98, 100gabaculine 330gingerol 76goniofufurone 350hippeastrine 333HMG-CoA synthase inhibitor 171ibuprophen 159lasiodiplodin 74leukotriene B4 348leukotriene B4 75LT~ 346

INDEX 425

LTB4 348malyngolide 98, 100medium-sized rings 343methylcarbapenem 162monomorine I 117muscone 19naproxen 159,388neocarzinostatin 343neooxazolom ycin 29nonactic acid 86, 88-90nucleoside derivatives 127O-methyljoubertiamine 331phyllanthocin 47physostigmine 281, 282Prelog-Djerassi lactone 335prostaglandins 404pyrethroids 344reticuline 383rout iennocin 356roxaticin 171showdomycin 116, 128sitophilate 322statine 171steroids 397sulcatol 266thienamycin 341trichodermol 329trichodiene 328trichothecene 328tylosin 323venturic idin 395vernolepin 291vitamin D3 369yashabushiketol 76zearalenone 74

TADDOL 214,247TagAld 272Takaya 159,160,168tamandron 336Tamm 53tamoxifen 336tandem reaction 54target molecule synthesis 368tartaric acid 41,136,139,367tartrate 15,244,247,339,373

-derived acetals 134terpenes 184tetrabutylammonium borohydride 67tetrahydrofarnesol 162tetralone 213, 352tetramethylammoniumtriacetoxyborohydride 88

tetramethylthreitol 247TFAE 245thalidomide 8thermitase 264

Thermoanaerobium brockii 266Thermoanaerobium brokil ADH 268thermodynamic control 76,105 ,108 ,121 ,237,244

thermolysin 262, 263thexylborane 201,207thienamycin 341thioesters 34thiophene 369third-generation asymmetric synthesis 3,242,397

Thornton 132threo-stereochemistry 242, 271threonine 173ThxBH 2 202, 203, 206-208tin 29,34,37,40,293tin(lI ) triflate 34titanium 4,9,15,129 ,135 ,138 ,177,231-259,367-369,373enolate s 240, 349tetrachloride 31,32,127 ,128tetraisopropoxide 367isopropoxide 134/ binapthol 386

titanocene 177,231,238TMEDA 186tol-BINAP 162(p-tolylsulfinyl)acetophenone 64transition metal catalysed hydrogenation

146-180transketolase 271transoid nt-complexes 326tributylvinyltin 293tricarbonyl-

(cyclohexadienyl)iron 328('16-arene)chromium 122,123(naphthalene)chromium 108,338chrom ium 108,337 ,338,349,350,352,

358,361,362iron 327,330, 333, 344, 346manganese 337,361

trichodermol 329trichodiene 328trichothecene 3282,2-trifluoro-I-(9'-anthracenyl)ethanol245

triisocampheyldiborane 183triphenylethane diol 33tris-s-butyl borohydride 68tropinone 116, 118Trost 299,304tryptophan 44Tsuji 299,302tylosin 323, 324

UEB Isis Chemie 155Uemura 16,298 ,352umpolung reactivity 321

426

valinol 50, 338VALPHOS 288van Koten 228vanadium 386Vederas 53venturicidin 392vernolepin 291vinyl sulfoxide 128Vitagliano 307vitamin

B3 168s, 168D 3 369E 252

Warren 56water soluable ligand 156,163,175Weissensteiner 295whole cells 263-271Widdowson 31Wilkinson's catalyst 146,164Wittig alkenation 78,79,328,347,348Wittig rearrangement 123,352,395

INDEX

Wittig-Horner alkenat ion 62,99working ligands 318

X-ray crystallography 13,61,105,106,119,128 ,136 ,233,234,236 ,238 ,247,299,306,307,308, 380

xylose 233

Yamaguchi 79Yamamoto 33,42,133, 136yashabushiketol 76yeast 271,272 ,401yeast alcohol dehydrogenase 266,268Yoshioka 254ytterbium 22

zearalenone 74zeaxanthin 268zinc 9,11 ,12,19 ,298

borohydride 67,68chloride 31

zirconium 32,231,253 ,254zirconocene 31, 32