257 Index a L-aminoacylase 246 absolute configuration 39, 75 amount of substance 12 –ofL-(+)-alanine 83 asymmetric atom 39 – by anomalous dispersion effect in X-ray asymmetric disequilibrating transformation crystallography 78 151 – by chemical correlation 79 asymmetric induction 143 – correlation strategies 80 – of second kind 151 – by direct methods 78 asymmetric synthesis 139 – extended sense of 77 asymmetric transformation –ofD-glyceraldehyde 39 – of second kind 151 –ofD-(+)-glyceraldehyde 77 asymmetric transformation of the second kind – by indirect methods 79 173 –ofD-(–)-lactic acid 81 atropisomer 44, 73 – methods of determination 78 atropisomerism 24, 71 – of natural glucose 78, 82 autocatalysis – by predictive calculation of chiroptical data – a special case of organocatalysis 234 79 autocatalytic effect –of(R,R)-(+)-tartaric acid 78, 82 – of a zinc complex 238 achiral bidentate reagent Avogadro constant 12 – purification of enantiomers with 149 axial chirality 39, 44 achiral stationary phase 95 achirality, achiral 24, 29 b aci form 113 Baeyer–Villiger oxidation acylase I 161 – enanatiotope selective 253 AD-mix- 229 – enzymatic 253 AD-mix- 229 – microbial 166 alcohol dehydrogenases – regio- and enanatiomer selective 253 – Prelog’s rule 252 baker’s yeast aldol reactions – regio-, enantiotope and diastereotope – catalyzed with chiral ionic liquid 238 selective reduction with 186 – catalytic, double enantiotope selective 238 bidentate achiral reagent 90 – completely syn diastereoselective 238 Bijvoet, J. M. 78 – stereoselctive 209 BINAL-H 212 allene 44 BINAP amide-imido acid tautomerism 112 – ruthenium complex of 214 amino acids biocatalysis 244 enantiopure, D-andL- 250 – advantages of 245 D-amino acid oxidase 100 – disadvantages of 245 Stereochemistry and Stereoselective Synthesis: An Introduction, First Edition. László Poppe and Mihály Nógrádi. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2016 by Wiley-VCH Verlag GmbH & Co. KGaA. Companion Website: www.wiley.com/go/poppe/stereochemistry 258 Index biocatalytic processes – by degradation of multiple asymmetric units – preparative 246 81 biotransformations – without influencing the asymmetric unit – enantiotope selective 251 81 – with more than one type of selectivity 186 – involving stereospecific reactions 83 biphenyl 71 –stereoconstructive 82 – o-substituted 72 chemical structure 8, 10 bond angle 8 –linearformula 6 bond length 8 –representation 6 bonding matrix 10 covalent bond 3 borane chemoselectivity 127, 130 – chiral, as reducing agents 216 – in biocatalysis 131 boranyl enolate – for manipulation of protecting groups 131 – antipodal 209 chiral aid – chiral 209 – important features of 141 bromobenzene – in selective synthesis of enantiomers 140 – regio- diastereo- and enantiotope- selective chiral aluminum-hydride reagent 211 oxidation of 253 chiral auxiliary groups 145, 151, 205 – enantiodivergent synthetic strategy with c 146 Candida antarctica lipase B 248, 250 – non-recoverable 145, 146 capillary electrophoresis 95 – of opposite stereoselectivity 205 carbon–carbon double bond – recoverable 145 – reduction by oxidoreductases 252 – significance of separation of the forming carboxylesterase 163, 179 diastereomers 147 Cartesian coordinate 8 –ofC2 symmetry 208 catalytic antibody chiral catalysis 213 – enantiotomer-selective retro-aldol reaction chiral catalyst by 249 –CBS.BH3complex 216 – enantiotope selective aldol reaction by – functions as a phase transfer catalyst 233 249 chiral chemical catalytic processes catalytic cycle – examples of 213 – of ketone reduction with chiral Ru-complex chiral cobalt complex 215 – with sodium tetrahydridoborate (NaBH4) – of reduction with chiral rhodium complex 218 214 chiral derivatizing agent 79, 89, 94, 95 catalytic diol formation chiral ionic liquid – stereoselective 228 – as organocatalyst 239 catalytic epoxidation chiral ligands 213 – enantiotope selective 219 chiral organocatalyst 233 catalytic hydrogenation –fromL-amino acids 233 – chiral (asymmetric) 213 chiral osmium–tetroxide complex catalyst catalytic systems 229 –ofC2 symmetry for Diels–Alder reaction chiral oxazoline 242 – enantiodivergent strategy from 206 center chiral pool 140, 203 – of asymmetry 39, 41, 43 chiral samarium catalyst 221 – of chirality 29, 41 chiral shift reagent 93 – of pseudoasymmetry 52, 53 chiral solvating agent 92 C==C double bond chiral solvent 92 – catalytic chiral reduction of 214 chiral stationary phase (CSP) 96 chemical bond 15 – amylose based 99 chemical correlation – cellulose based 99 – by configurational correlation 83 – Chirasil-Val 97 Index 259 – cyclodextrin based 98 – relative population of 69 – efficiency of separation on 96 conformer 67 – phases in both configurations 96 constitution 23 –Pirkletype 98 constitutional isomer 26 –proteinbased 99 crystallization induced asymmetric – reversed elution order 96 transformations (CIAT) 150 – shape recognizing polymer 99 – involving diastereotopic interactions 149 chirality transfer 145, 149, 203, 205 crystallization induced dynamic resolution – enantioselective catalytic 213 (CIDR) 172 chirality, chiral 24, 27 – with a chiral additive 173 – at microscopic level 29 – enantiomer selective variant 172 – axial 39, 44 cumulene, E/Z 44 – center of 29, 39 cyclodextrins 98 –central 43 cyclohexanone monooxygenase (CHMO) – material assemblies 29 253 –planar 46 cyclopropanation, stereoselective chromatography 94 – of allyl alcohol derivatives 240 – on diastereoselective stationary phase 94, 95 d chromophore 79 deracemization 151, 175 chymotrypsin (CTR) diastereomer 27 – hydrolysis by 186 diastereomer selectivity 128, 141 C.I.P. system – types of 141 – sequence rule 41 diastereoselective resolution 151 classic resolution 154 diastereoselective stationary phase 94 coenzymes 244, 245 diastereoselectivity 128 –NAD(P)+ and NAD(P)H 251 diastereotope selective methods 128, 142 – regeneration of 251 – with an achiral reagent 143 cofactor 245 – controlled by an auxiliary group 204 concerted diastereotope selectivity – between diastereotopic faces 143 – of chiral molecules 208 – in biotransformations 153 configuration 23, 27, 28, 75 – between specific parts of a molecule configurational inversion 142 – of unwanted enantiomer 156 – for preparation of pure enantiomers 203 conformation 24, 27, 67 diastereotope selective reaction –anticlinal 70 – of amides formed with (S)-prolinol 205 – antiperiplanar 70 diastereotopic –ofbiphenyl 71 – faces 37, 54, 143 –ofn-butane 70 – groups 34, 142 – of chlorocyclohexane 14 diastereotopic faces – of cyclohexane 27 – selective biotransformation of 153 – of 1,2-dichloroethane 70 diastereotopic groups –eclipsed 67 – selective biotransformation of 153 –energyof 70 Diels-Alder reaction – of ethane 67 – stereoselective, catalytic 240 –gauche 70 diethyl-zinc 232 –open 67 differential scanning calorimetry (DSC) 102 –synclinal 70 dihedral angle 10 – synperiplanar 70 dioxygenase conformational change 67 – enantiotope selective and cis-specific conformational range 71 dihydroxylation by 253 conformational state double asymmetric induction 145, 208, 220 –achial 68 double bond – chial 68 – hindered rotation 43 260 Index dynamic kinetic resolution 156 – determination with bidentate achiral reagent – of 5-benzylhydantoin 251 90 – with biocatalysis 168 – determination with chiral derivatizing agent – using chemical systems 167 89 – DKR 151, 166 – determination with chiral solvent 92 – enzyme catalyzed 250 – by kinetic methods based on enantiomer – enzyme catalyzed, industrial application selectivity 99 250 – methods for determination 87, 88 – involving acid-catalyzed racemization 169 enantiomeric excess 87 – involving base-catalyzed racemization 168 – in enantiotope selective reaction 176 – involving biocatalytic racemization 171 – in kinetic resolution 157 – involving metal-catalyzed racemization – of the remaining enantiomer in kinetic 170 resolution 158 – with racemization by ring opening 169 enantiomeric products – by kinetic methods using catalysts 201 e – by stoichiometric methods 201 electrostatic potential surface 13 enantiomeric purity 87 enamine form 111 enantiomeric recognition enantiodivergent reactions 185 –principleof 96 enantiodivergent strategy 146 enantiomeric relationship 69 – for stereoselective alkylation 206 enantiomers enantiodivergent transformations 176 – purification of, with the aid of an achiral enantiomer 27 bidentate reagent 149 – chemical behavior of 27 – selective synthesis of 139 – scalar physical properties of 27 enantioselectivity 128 – vectorial physical properties of 27 enantiotope selective methods 128, 175, 211 enantiomer selective 128 – in biocatalytic systems 179 enantiomer selective process – reduction of carbon-carbon double bond, – irreversible 156 microbial 181 – reversible 156 – of chemical systems 177 enantiomer selectivity 128, 155 – degree of 176 –(E) 156 – independent of conversion 176 – degree of 155, 156 – intransformationofenantiotopicfaces 175 – in irreversible process 155, 156 – in transformation of enantiotopic groups enantiomeric composition 175 – by chromatography on chiral stationary enantiotope selective oxidation phase (CSP) 96 – by a dioxygenase 253 – by chromatography on diastereoselective enantiotope selective transformations stationary phase 94 – consequences of opposing 182 – determination based on diastereotopicity enantiotopic 89 – faces 36, 54, 175 – determination based on isotope dilution – groups 31, 175 102 enantiotopic groups – determination by chromatographic methods – transformations by biocatalysis 179 94 energy barrier