Series Preface ............................................... xvii
Preface to Volume 5 ........................................... xix
Abbreviations ................................................. xxi
1. Industrial Catalysts for Regio- or Stereo-Selective
Oxidations and Reductions. A Review of Key Technologies
and Targets .................................................. 1
John Whittall
1.1. Introduction ............................................ 2
1.2. Reduction of Carbon-Carbon Double Bonds ................. 3
1.2.1. Privileged structures: α-amino acids and
itaconic acids ................................... 4
1.2.2. β-Amino acids .................................... 5
1.2.3. α-Alkyl substituted acids ........................ 6
1.2.4. α-Alkoxy substituted acids ....................... 8
1.2.5. Unsaturated nitriles ............................. 9
1.2.6. Alkenes and allyl alcohols ...................... 10
1.2.7. α,β-Unsaturated aldehyde reduction .............. 10
1.3. Ketone and Imine Reduction ............................. 12
1.3.1. Catalytic hydrogenation of ketones and imines ... 12
1.3.2. Asymmetric transfer hydrogenation (ATH)
catalysts ....................................... 15
1.3.3. Modified borane reagents ........................ 20
1.3.4. Biocatalysts (alcohol dehydrogenases and
ketoreductases) ................................. 21
1.4. Oxidation .............................................. 23
1.4.1. Sharpless chiral epoxidation of allyl
alcohols ........................................ 23
1.4.2. Dioxirane catalyzed epoxidation ................. 23
1.4.3. Amines and iminium salts ........................ 25
1.4.4. Phase transfer catalysts ........................ 25
1.4.5. The Julia-Colonna method (polyleucine
oxidation) ...................................... 26
1.4.6. Organocatalytic a-hydroxylation of ketones ...... 27
1.4.7. Baeyer-Villiger oxidation ....................... 27
1.4.8. Chiral sulfoxides ............................... 28
References .................................................. 29
2. Asymmetric Hydrogenation of Alkenes, Enones, Ene-Esters
and Ene-Acids ............................................... 35
2.1. (5)-2,2'-Bis{[di(4-methoxyphenyl)phosphinyl]oxy}-
5,5',6,6',7,7', 8,8'-octahydro-l,l'-binaphthyl as
a ligand for rhodium-catalyzed asymmetric
hydrogenation .......................................... 36
Ildiko Gergely, Csaba Hegedüs and Jozsef Bakos
2.1.1. Synthesis of (5)-5,5',6,6',7,7',8,8'-
Octahydro-l,l'-bi-2-naphthol .................... 37
2.1.2. Synthesis of (S)-2,2'-Bis{[ldi(4-methoxyphenyl)
phosphinyl]oxy}-5,5',6,6',7,7',8,8'-
octahydro-1, r-binaphthyl ....................... 38
2.1.3. Asymmetric hydrogenation of Dimethyl
itaconate ....................................... 40
Conclusion ............................................. 41
References ............................................. 41
2.2. Synthesis and application of phosphinite oxazoline
iridium complexes for the asymmetric hydrogenation
of alkenes ............................................. 42
Frederik Menges and Andreas Pfaltz
2.2.1. Synthesis of (4S,5S)-2-(5-MethyI-2-phenyl-4,
5-dihydro-oxazol-4-yl)-l,3-diphenyl-
propan-2-ol ..................................... 42
2.2.2. Synthesis of (4S,5S)-0-[1-Benzyl-1-
(5-methyl-2-phenyl-4, 5-dihydro-oxazol-4-yl)
-2-phenyl-ethyl]-diphenylphosphinite ............ 43
2.2.3. Synthesis of (4S,5S)-l(η4-l,5-
Cyclooctadiene)-{2-(2-phenyl-5-methyl-4,5-
dihydro-oxazol-4-yl)-1,3-diphenyl-2-
diphenylphosphinite-propane} iridium(I)]-
tetrakis[3, 5-bis(trifluoromethyl)
phenyl]borate ................................... 45
2.2.4. Asymmetric hydrogenation of trans-α-
Methylstilbene .................................. 46
Conclusion ............................................. 47
References ............................................. 48
2.3. Synthesis and application of heterocyclic phosphine
oxazoline (HetPHOX) iridium complexes for the
asymmetric hydrogenation of alkenes .................... 48
Frederik Menges and Pier Giorgio Cozzi
2.3.1. Synthesis of (4S)-tert-Butyl-2-(thiophene-2
-yl)-4,5-dihydrooxazole ......................... 49
2.3.2. Synthesis of (4S)-tert-Butyl-2-(3-
diphenylphosphino-thiophene-2-yl)-4,5-
dihydrooxazole .................................. 50
2.3.3. Synthesis of (4S)-[η4-l,5-Cyclooctadiene)-
{4-tert-butyl-2-(3-diphenylphosphino-
thiophene-2-yl)-4,5-dihydrooxazole} iridium(I)
-tetrakis[3,5-bis(trifluoromethyl)phenyl]
borate .......................................... 52
2.3.4. Asymmetric hydrogenation of trans-α-
Methylstilbene .................................. 53
Conclusion ............................................. 54
References ............................................. 54
2.4. (R)-2,2',6,6'-Tetramethoxy-bis[di(3,5-
dimethylphenyl)phosphinol-3,3'-bipyridine [(R)-Xyl-
P-Phos] as a ligand for rhodium-catalyzed asymmetric
hydrogenation of α-dehydroamino acids .................. 55
Jing Wu and Albert S.C. Chan
2.4.1. Synthesis of 3-Bromo-2,6-dimethoxypyridine ...... 55
2.4.2. Synthesis of Bis(3,5-dimethylphenyl)phosphine
chloride ........................................ 56
2.4.3. Synthesis of 3-Bromo-2,6-dimethoxy-4-di(3,
5-dimethylphenyl) phosphinopyridine ............. 57
2.4.4. Synthesis of 3-Bromo-2,6-dimethoxy-4-di(3,
5-dimethylphenyl) phosphinopyridine ............. 59
2.4.5. 2,2',6,6'-[Tetramethoxy-bisldi(3,5-
dimethylphenyl)phosphinoyl]-3,3'-bipyridine ..... 60
2.4.6. Optical resolution of (+-)-6 with (-) or (+)-
2,3-O,O'-Dibenzoyltartaric acid monohydrate
[(R)-6 or (S)-6)] ............................... 61
2.4.7. (R)-2,2',6,6'-Tetramethoxy-bisldi(3,5-
dimethylphenyl)phosphinol-3,3'-bipyridine
[(R)-Xyl-P-Phos, (R)-l] ......................... 62
2.4.8. Preparation of the stock solution of [Rh(R-
Xyl-P-Phos)(COD)]BF4 ............................ 63
2.4.9. A typical procedure for the asymmetric
hydrogenation of methyl (Z)-2-
Acetamidocinnamate .............................. 64
References ............................................. 65
2.5. (R,R)-2,3-Bis(tert-butylmethylphosphino)quinoxaline
(QuinoXP*) as a ligand for rhodium-catalyzed
asymmetric hydrogenation of prochiral amino acid
and amine derivatives .................................. 65
Tsuneo Imamoto and Aya Koide
2.5.1. Synthesis of (R)-tert-Butyl(hydroxymethyl)
methylphosphine-borane .......................... 66
2.5.2. Synthesis of (R)-Benzoyloxy(ter/-butyl)
methylphosphine-borane .......................... 67
2.5.3. Synthesis of (S)-tert-Butylmethylphosphine-
borane .......................................... 69
2.5.4. (R,R)-2,3-Bis(tert-butylmethylphosphino)
quinoxaline (QuinoxP*) .......................... 70
2.5.5. Asymmetric hydrogenation of Methyl (E)-3-
acetylamino-2-butenoate catalyzed by Rh(I)
-(R,R)-2,3-Bis(tert-butylmethylphosphino)
quinoxaline ..................................... 71
Conclusion ............................................. 72
References ............................................. 73
2.6. Rhodium-catalyzed asymmetric hydrogenation of
indoles ................................................ 73
Ryoichi Kuwano and Masaya Sawamura
2.6.1. Synthesis of (R)-2-[(S)-l-(Dimethylamino)
ethyl]-l-iodoferrocene .......................... 73
2.6.2. Synthesis of (R)-2-[(S)-l-(Diphenylphosphinyl)
ethyl]-1-iodoferrocene .......................... 75
2.6.3. Synthesis of (R,R)-2,2'-Bis[(S)-1-
(diphenylphosphinyl)ethyl]-1, l''-biferrocene ... 78
2.6.4. Synthesis of (R,R)-2,2'-Bis[(S)-1 -
(diphenylphosphino)ethyl]-1, l''-biferrocene
[abbreviated to (S,S)-(R,R)-PhTRAP] ............. 80
2.6.5. Catalytic asymmetric hydrogenation of N-
Acetyl-2-butylindole ............................ 82
2.6.6. Catalytic asymmetric hydrogenation of 3-
Methyl-N-(p-toluenesulfonyl)indole .............. 84
Conclusion ............................................. 85
References ............................................. 86
3. Asymmetric Reduction of Ketones ............................. 87
3.1. (R,R)-Bis(diphenylphosphino)-l,3-diphenylpropane
as a versatile ligand for enantioselective
hydrogenations ......................................... 89
Natalia Dubrovina and Armin Börner
3.1.1. Synthesis of (S,S)-1,3-Diphenylpropane-1,3-
diol ............................................ 89
3.1.2. Synthesis of (S,S)-Methanesulfonyloxy-1,
3-diphenylpropane-1,3-diol ...................... 91
3.1.3. Synthesis of (R,R)-Bis(diphenylphosphino)
-l,3-diphenylpropane ............................ 91
Conclusion ............................................. 93
References ............................................. 93
3.2. Synthesis of both enantiomers of 1-Phenylethanol
by reduction of acetophenone with Geotrichum
candidum IFO 5767 ...................................... 93
Kaoru Nakamura, Mikio Fujii and Yoshiteru Ida
3.2.1. Cultivation of G. candidum IFO 5767 ............. 94
3.2.2. Synthesis of (S)-1 -Phenylethanol ............... 95
3.2.3. Synthesis of (R)-1 -Phenylethanol ............... 95
Conclusion ............................................. 97
References ............................................. 97
3.3. Titanocene-catalyzed reduction of ketones in the
presence of water. A convenient procedure for the
synthesis of alcohols via free-radical chemistry ....... 97
Antonio Rosales, Juan M. Cuerva and J. Enrique Oltra
3.3.1. Titanocene-catalyzed reduction of
Acetophenone in the presence of water ........... 98
3.3.2. Titanocene-catalyzed synthesis of Methyl
4-deuterio-4-phenyl-4-hydroxybutanoate .......... 99
References ............................................ 100
3.4. Xyl-tetraPHEMP: a highly efficient biaryl ligand in
the [diphosphine RuCl2 diamine]-catalyzed
hydrogenation of simple aromatic ketones .............. 101
Paul H. Moran, Julian P. Henschke, Antonio Zanotti-
Gerosa and Ian C. Lennon
3.4.1. Synthesis of Tri(3,5-dimethylphenyl)
phosphine oxide ................................ 102
3.4.2. Synthesis of Bis(3,5-dimethylphenyl)-(2-
iodo-3, 5-dimethylphenyl)phosphine oxide ....... 103
3.4.3. Synthesis of rac-4,4',6,6'-Tetramethyl-2,2'-
bis[bis(3, 5-dimethylphenyl)phosphinoyl]-
biphenyl ....................................... 105
3.4.4. Synthesis of rac-4,4',6,6'-Tetramethyl-2,2'-
bis[bis(3, 5-dimethylphenyl)phosphino]-
biphenyl [abbreviated to (rac)-Xyl-
tetraPHEMP] .................................... 106
3.4.5. Synthesis of [(R)-N,N-Dimethyl(l-methyl)
benzyIaminato-C2,N]-{rac-4,4',
6,6'-tetramethyl-2,2'-bis[bis(3,5-
dimethylphenyl) phosphino]-biphenyl}-
palladium(II) tetrafluoroborate and
separation of the diastereomers ................ 107
3.4.6. Synthesis of (S)-4,4',6,6'-Tetramethyl-2,
2'-bis[bis(3, 5-dimethylphenyl)phosphino]
-biphenyl: [abbreviated to (S)-Xyl-
tetraPHEMP] and (R)-4,4',6,6'-Tetramethyl-2,
2'-bis[bis(3,5-dimethylphenyl)phosphino]-
biphenyI [abbreviated to (R)-Xyl-tetraPHEMP] ... 108
3.4.7. Synthesis of [(R)-Xyl-tetraPHEMP RuCl2
(R,R) -DPEN] and [(S)-Xyl-tetraPHEMP RuCl2
(S,S)-DPEN] .................................... 110
3.4.8. Reduction of Acetophenone using [(S)-Xyl-
tetraPHEMP RuCl2 (S,S)-DPEN] as a
precatalyst .................................... 1ll
Conclusion ............................................ 112
References ............................................ 112
3.5. N-Arenesulfonyl- and N-Alkylsulfamoyl-l,2-
diphenylethylenediamine ligands for ruthenium-
catalyzed asymmetric transfer hydrogenation of
activated ketones ..................................... 113
Michel (Massoud S.) Stephan and Barbara Mohar
3.5.1. Synthesis of N-Arenesulfonyl-1,2-
diphenylethylenediamines ....................... 113
3.5.2. Preparation of Ru(II)-N-arenesulfonyl-l,
2-diphenylethylenediamine complexes ............ 114
3.5.3. Asymmetric transfer hydrogenation of Ethyl
benzoylacetate ................................. 115
Conclusion ............................................ 116
References ............................................ 116
3.6. The synthesis and application of BrXuPHOS: a novel
monodentate phosphorus ligand for the asymmetric
hydrogenation of ketones .............................. 116
Martin Wills, Yingjian Xu, Garden Docherty and Gary
Woodward
3.6.1. Synthesis of (S)-BrXuPHOS ...................... 117
3.6.2. Synthesis of (S,S,SS)-BrXuPHOS-Ru-DPEN ......... 119
3.6.3. General procedure of asymmetric
hydrogenation of acetophenone .................. 120
Conclusion ............................................ 121
Acknowledgement ....................................... 121
References ............................................ 121
3.7. In Situ formation of ligand and catalyst:
application in ruthenium-catalyzed enantioselective
reduction of ketones .................................. 121
Jenny Wettergren and Hans Adolfsson
3.7.1. Synthesis of (S)-3-Fluoro-l-phenylethanol ...... 122
Conclusion ............................................ 123
References ............................................ 124
3.8. Synphos and Difluorphos as ligands for ruthenium-
catalyzed hydrogenation of alkenes and ketones ........ 125
Severine Jeulin, Virginie Ratovelomanana-Vidal and
Jean-Pierre Genet
3.8.1. Synthesis of [RuCl((S)-SYNPHOS)(p-cymene)]Cl ... 125
3.8.2. Synthesis of [RuCl((S)-DIFLUORPHOS)
(p-cymene)]Cl .................................. 126
3.8.3. Synthesis of [RuI((S)-DIFLUORPHOS)
(p-cymene)]I ................................... 127
3.8.4. Synthesis of [NH2R2][(RuCl(P*P))2(μ-Cl)3]
P*P = SYNPHOS or DIFLUORPHOS and R = Me
or Et .......................................... 127
3.8.5. Synthesis of [NH2Me2][RuCl-(S)-DlFLUORPHOS]2
μ-Cl)3 ......................................... 128
3.8.6. Synthesis of in situ generated [RuBr2
((S)-SYNPHOS)] and [RuBr2((S)-
DIFLUORPHOS)] .................................. 129
Conclusion ............................................ 131
References ............................................ 131
3.9. An arene ruthenium complex with polymerizable side
chains for the synthesis of immobilized catalysts ..... 132
Estelle Burri, Silke B. Wendicke, and Kay Severin
3.9.1. Synthesis of 2-Methyl-cyclohexa-2,5-
dienecarboxylic acid 2-(2-methyl-acryloyloxy)
-ethyl ester ................................... 133
3.9.2. Synthesis of [η6 -(2-Methyl-benzoic acid
2-(2-methyl-acryloyloxy)-ethyl ester)RuCl2]2 ... 134
Conclusion ............................................ 135
References ............................................ 135
3.10.Selective reduction of carbonyl group in β,γ
-unsaturated α-alpha-ketoesters by transfer
hydrogenation with Ru-(p-cymene)(TsDPEN) .............. 135
Minjie Guo, Dao Li, Yanhui Sun and Zhaoguo Zhang
3.10.1.Synthesis of Di-μ-chloro-bis[chloro(η6
-1-isopropyl-4-methyl-benzene)ruthenium(II) .... 136
3.10.2.Synthesis of (+-)-Monotosylate-l,
2-diphenyl-1,2-ethylenediamine ................. 136
3.10.3.Synthesis of Ru complex Ru(p-cymene)(TsDPEN) ... 138
3.10.4.Ru-TsDPEN catalyzed transfer hydrogenation
reaction of β, γ-unsaturated-α-ketoesters ...... 139
Conclusion ............................................ 140
References ............................................ 141
3.11.Preparation of polymer-supported Ru-TsDPEN
catalysts and their use for the enantioselective
synthesis of (S)-fluoxetine ........................... 141
Liting Chai, Yangzhou Li and Quanrui Wang
3.11.1.Synthesis of the supported ligand 9 ............ 141
3.11.2.Synthesis of ligand 17 ......................... 148
3.11.3.General procedure for asymmetric transfer
hydrogenation .................................. 150
3.11.4.Preparation of (S)-Fluoxetine hydrochloride .... 151
Conclusion ............................................ 154
References ............................................ 154
3.12.Polymer-supported chiral sulfonamide-catalyzed
reduction of β-keto nitriles: a practical synthesis
of (R)-Fluoxetine ..................................... 155
Guang-yin Wang and Gang Zhao
3.12.1.Synthesis of (R)-3-Amino-l-phenyl-
propan-l-ol .................................... 155
3.12.2.Synthesis of (R)-ethyl 3-hydroxy-3-
phenylpropylcarbamate .......................... 156
3.12.3.Synthesis of (R)-3-(Methylamino)-1-
phenylpropan-1-ol .............................. 157
3.12.4.Synthesis of (R)-Fluoxetine .................... 158
Conclusion ............................................ 159
References ............................................ 159
4. Imine Reduction and Reductive Amination .................... 161
4.1. Metal-free reduction of imines: enantioselective
Brønsted acid-catalyzed transfer hydrogenation
using chiral BINOL-phosphates as catalysts ............ 162
Magnus Rueping, Erli Sugiono, Cengiz Azap and
Thomas Theissmann
4.1.1. Synthesis of (R)-2,2'-Bis-methoxymethoxy-
[1,1]binaphthalene (MOM-BINOL) ................. 162
4.1.2. Synthesis of (R)-3,3'-Diiodo-2,2'-bis
(methoxymethoxy)-1, 1'-binaphthalene ........... 164
4.1.3. Synthesis of 3,3'-Bis-(3,5'-bis-
trifluoromethyl-phenyl)-2,2'-
bismethoxymethoxy [l,l'-binaphthalene] ......... 165
4.1.4. Synthesis of (R)-3,3'-[3,5-Bis
(trifluoromethyl)phenyl]-l,l'-
binaphthylphosphate ............................ 166
4.1.5. General procedure for the transfer
hydrogenation of ketimines ..................... 167
4.1.6. Synthesis of [1-(2,4-Dimethyl-phenyl)-ethyl]
-(4-methoxy-phenyl)-amine ...................... 167
Conclusion ............................................ 168
References ............................................ 170
4.2. Metal-free Brønsted acid-catalyzed transfer
hydrogenation: enantioselective synthesis of
tetrahydroquinolines .................................. 170
Magnus Rueping, Thomas Theissmann and Andrey
P. Antonchick
4.2.1. General procedure for the transfer
hydrogenation of quinolines .................... 170
4.2.2. Synthesis of 7-Chloro-4-phenyl-l,2,3,4-
tetrahydroquinoline ............................ 172
4.2.3. Synthesis of (S)-2-Phenyl-l,2,3,4-
tetrahydroquinoline ............................ 172
4.2.4. Synthesis of (R)-2-(2-(Benzo[1,3]dioxol-5-
yl)ethyl)-1,2,3,4-tetrahydro-quinoline ......... 173
Conclusion ............................................ 174
References ............................................ 174
4.3. A highly stereoselective synthesis of 3α-Amino-23,
24-bisnor-5α-cholane via reductive amination .......... 175
Sharaf Nawaz Khan, Nam Ju Cho and Hong-Seok Kim
4.3.1. Synthesis of Tris[(2-ethylhexanoyl)oxy]
borohydride .................................... 177
4.3.2. Synthesis of 3α-Acetamino-23,24-bisnor-5α-
cholane ........................................ 177
4.3.3. Synthesis of 3α-N-1-[N(3-[4-Aminobutyl])
-1,3-diaminopropane]-23,24-bisnor-5α-
cholane ........................................ 179
Conclusion ............................................ 181
Acknowledgements ...................................... 181
References ............................................ 181
5. Oxidation of Primary and Secondary Alcohols ................ 183
5.1. Copper(ll) catalyzed oxidation of primary alcohols
to aldehydes with atmospheric oxygen .................. 183
Surihabu Jammi and Tharmalingan Punniyamurthy
5.1.1. Synthesis of copper(II) complex 1 .............. 184
5.1.2. Typical procedure for the oxidation of
primary alcohols to aldehydes .................. 185
Conclusion ............................................ 186
References ............................................ 187
5.2. Solvent-free dehydrogenation of secondary alcohols
in the absence of hydrogen abstractors using
Robinson's catalyst ................................... 187
G.B.W.L. Ligthart, R.H. Meijer, J. v. Buijtenen,
J. Meuldijk, J.A.J.M. Vekemans and L.A. Hulshof
5.2.1. Dehydrogenation of 2-Octanol using
Ru(OCOCF3)2(CO)(PPh3)2 as a catalyst ........... 187
Conclusion ............................................ 188
References ............................................ 188
5.3. 2-Iodoxybenzoic acid (IBX)/n-Bu4NBr/CH2Cl2-H2O:
a mild system for the selective oxidation of
secondary alcohols .................................... 188
Krisada Kittigowittana, Manat Pohmakotr, Vichai
Reutrakul and Chutima Kuhakarn
5.3.1. Synthesis of 1-Hydroxy-5-decanone .............. 189
Conclusion ............................................ 192
References ............................................ 192
6. Hydroxylation, Epoxidation and Related Reactions ........... 193
6.1. Proline-catalyzed α-aminoxylation of aldehydes and
ketones ............................................... 194
Yujiro Hayashi and Mitsuru Shoji
6.1.1. Synthesis of (R)-2-Anilinoxypropanol ........... 195
6.1.2. Synthesis of (R)-7-Anilinoxy-l,4-dioxaspiro
[4.5]decan-8-one ............................... 196
Conclusion ............................................ 197
References ............................................ 198
6.2. Ru/Silia* Cat*TMTEMPO-mediated oxidation
of alkenes to α-hydroxyacids .......................... 199
Rosaria Ciriminna and Mario Pagliaro
6.2.1. Synthesis of Silia&42;Cat&42;TMTEMPO ............ 199
6.2.2. Synthesis of 2-(4-Chlorophenyl)-1,2-
propanediol .................................... 201
6.2.3. Synthesis of 2-(4-Chlorophenyl)-1,2-
hydroxypropanoic acid .......................... 202
Conclusion ............................................ 204
References ............................................ 204
6.3. Catalytic enantioselective epoxidation of trans-
disubstituted and trisubstituted alkenes with
arabinose-derived ulose ............................... 204
Tony K.M. Shing, Gulice Y.C. Leung and To Luk
6.3.1. Synthesis of 2',3'-Diisobutyl acetal ........... 205
6.3.2. Synthesis of ulose ............................. 206
6.3.3. Asymmetric epoxidation of trans-α-
Methylstilbene using ulose as catalyst
at 0°C ......................................... 208
Conclusion ............................................ 209
References ............................................ 210
6.4. VO(acac)2/TBHP catalyzed epoxidation of 2-(2-
Alkenyl)phenols highly regio- and diastereoselective
oxidative cyclisation to 2,3-Dihydrobenzofuranols
and 3-Chromanols ...................................... 211
Alessandra Lattanzi and Arrigo Scettri
6.4.1. VO(acac)2/TBHP catalyzed epoxidation of 2-
(3,7-Dimethyl-octa-2,6-dienyl)-phenol .......... 212
6.4.2. VO(acac)2/TBHP/TFA catalyzed oxidative
cyclization of 2-(3,7-Dimethyl-octa-2,6-
dienyl)-phenol ................................. 213
Conclusion ............................................ 214
References ............................................ 214
6.5. An Oxalolidinone ketone catalyst for the asymmetric
epoxidation of cis-olefins ............................ 215
David Goeddel and Yian Shi
6.5.1. Amadori rearrangement to give 1-
Dibenzylamino-1-deoxy-D-fructose ............... 215
6.5.2. Acetal protection of 1-Dibenzylamino-l-
deoxy-D-fructose ............................... 216
6.5.3. Hydrogenation of the Dibenzylamine ............. 217
6.5.4. Phosgene cyclization of aminoalcohol ........... 218
6.5.5. Alcohol oxidation .............................. 220
6.5.6. Synthesis of ketone 2 .......................... 221
6.5.7. Asymmetric epoxidation of cis-β-
Methylstyrene .................................. 222
Conclusion ............................................ 223
References ............................................ 224
6.6. α-Fluorotropinone immobilised on silica: a new
stereoselective heterogeneous catalyst for
epoxidation of alkenes with oxone ..................... 225
Giovanni Sartori, Alan Armstrong, Raimondo Maggi,
Alessandro Mazzacani, Raffaella Sartorio, France
Bigi and Belen Dominguez-Fernandez
6.6.1. Synthesis of silica KG-60-supported
enantiomerically enriched α-Fluorotropinone .... 225
6.6.2. Synthesis of enantiomerically enriched
epoxides ....................................... 226
Conclusion ............................................ 227
References ............................................ 228
6.7. Asymmetric epoxidation catalyzed by novel azacrown
ether-type chiral quaternary ammonium salts under
phase-transfer catalytic conditions ................... 228
Kazushige Hori, Keita Tani and Yasuo Tohda
6.7.1. Synthesis of precursor of the azacrown ether ... 229
6.7.2. Synthesis of the azacrown ether ................ 230
6.7.3. Synthesis of the azacrown ether-type
quaternary ammonium salt ....................... 232
6.7.4. Asymmetric epoxidation of (E)-Chalcone
catalyzed by the azacrown ether-type
quaternary ammonium salt as chiral PTC ......... 233
Conclusion ............................................ 234
References ............................................ 235
6.8. Enantioselective epoxidation of olefins using phase
transfer conditions and a chiral lazepinium]
[TRISPHAT] salt as catalyst ........................... 235
Jerome Vachon, Celine Perollier, Alexandre Martinez
and Jerome Lacour
6.8.1. Enantioselective epoxidation of 1-Phenyl-3,
4-dihydronaphthalene ........................... 236
Conclusion ............................................ 238
References ............................................ 239
6.9. Catalytic asymmetric epoxidation of α,β-
unsaturated esters promoted by a Yttrium-
biphenyldiol complex .................................. 239
Masakatsu Shibasaki, Hiroyuki Kakei and Shigeki
Matsunaga
6.9.1. Synthesis of (αS,R)-6,6'-l[Propylene)dioxy]
biphenyl-2,2'-diol ............................. 240
6.9.2. Synthesis of (αS,R)-2,2-[Oxybis(ethylene)
dioxy]-6,6'-[(propylene)dioxy]biphenyl ......... 242
6.9.3. Synthesis of (S)6,6'-[Oxybis(ethylene)dioxy]
biphenyl-2,2'-diol ............................. 243
6.9.4. Enantiomeric enrichment of (S)-6,6'-
[Oxybis(ethylene)dioxy]biphenyl-2,2'-diol ...... 244
6.9.5. Catalytic asymmetric epoxidation of α,β
unsaturated esters ............................. 246
References ............................................ 248
6.10.Catalytic enantioselective epoxidation of α,β-
enones with a binol-zinc-complex ...................... 249
Ana Minatti and Karl Heinz Dötz
6.10.1.Synthesis of (E)-(2S,3R)-Phenyl-(3-
phenyloxiran-2-yl)methanone .................... 249
Conclusion ............................................ 250
References ............................................ 251
6.11.Asymmetric epoxidation of Phenyl-2-(3'-
pyridylvinyl)sulfone using polyleucine hydrogen
peroxide gel .......................................... 251
Mike R. Pitts and John Whittall
6.11.1.Preparation of polyleucine-hydrogen
peroxide gel ................................... 252
6.11.2.Synthesis of Phenyl-2-(3'-pyridylvinyl)
sulfone (2) .................................... 252
References ............................................ 254
7. Oxidation of Ketones to Lactones or Enones ................. 255
7.1. Synthesis of 2-(Phosphinophenyl)pyrindine ligand
and its application to palladium-catalyzed
asymmetric Baeyer-Villiger oxidation of prochiral
cyclobutanones ........................................ 256
Katsuji Ito and Tsutomu Katsuki
7.1.1. Synthesis of (7R)-2-(2-Hydroxyphenyl)-7-
isopropyl-6,7-dihydro-5H-1-pyrindine ........... 256
7.1.2. 2-[2-(Diphenylphosphinoyl)phenyl]-7-
isopropyl-6,7-dihydro-5H-l -pyrindine .......... 258
7.1.3. 2-[2-(Diphenylphosphanyl)phenyl]-7-
isopropyl-6,7-dihydro-5H-l -pyrindine .......... 259
7.1.4. Asymmetric Baeyer-Villiger oxidation of
3-Phenylcyclobutanone .......................... 261
Conclusion ............................................ 262
References ............................................ 263
7.2. (D)-Codeinone from (D)-Dihydrocodeinone via the use
of modified o-iodoxybenzoic acid (IBX). A convenient
oxidation of ketones to enones ........................ 263
Paul Mather and John Whittall
7.2.1. Synthesis of IBX ............................... 264
7.2.2. Synthesis of codeinone ......................... 264
References ............................................ 266
8. Oxidative C-C Coupling ..................................... 267
8.1. Enantioselective oxidative coupling of 2-Naphthols
catalyzed by a novel chiral vanadium complex .......... 267
Nan-Sheng Xie, Quan-Zhong Liu, Zhi-Bin Luo,
Liu-Zhu Gong, Ai-Qiao Mi and Yao-Zhong Jiang
8.1.1. Synthesis of 3,3-Diformyl-2,2'-biphenol ........ 268
8.1.2. Synthesis of chiral vanadium complexes ......... 270
8.1.3. Catalytic oxidative coupling of 7-Alkoxy-l-
naphthols by chiral vanadium complexes ......... 271
Reference ............................................. 272
8.2. Catalytic oxidative cross-coupling reaction of
2-Naphthol derivatives ................................ 273
Shigeki Habaue and Tomohisa Temma
8.2.1. Synthesis of Methyl 2,2'-dihydroxy-1,1'-
binaphthalene-3-carboxylate .................... 273
Conclusion ............................................ 274
References ............................................ 275
8.3. Oxidative coupling of benzenes with α,β-
unsaturated aldehydes by Pd(OAc)2/HPMoV/O2 system ..... 275
Tomoyuki Yamada, Satoshi Sakaguchi and Yasutaka Ishii
8.3.1. Synthesis of Cinnamaldehyde .................... 276
Conclusion ............................................ 278
References ............................................ 278
9. Oxidation of Sulfides and Sulfoxides ....................... 279
9.1. The first example of direct oxidation of sulfides
to sulfones by an osmate-molecular oxygen system ...... 280
Boyapati M. Choudary, Chinta Reddy, V. Reddy,
Billakanti V. Prakash, Mannepalti L. Kantam and
B. Sreedhar
9.1.1. Synthesis of osmate exchanged Mg-Al layered
double hydroxides (LDH-OsO4) ................... 280
9.1.2. Synthesis of Methyl phenyl sulfone or
Methylsulfonylbenzene .......................... 281
Conclusion ............................................ 282
References ............................................ 283
9.2. Selective oxidation of sulfides to sulfoxides and
sulfones using hydrogen peroxide in the presence of
zirconium tetrachloride ............................... 283
Kiumar Bahrami
9.2.1. Oxidation of Benzyl 4-bromobenzyl sulfide
to Benzyl 4-bromobenzyl sulfoxide using H2O2
in the presence of zirconium tetrachloride ..... 284
9.2.2. Oxidation of Benzyl 4-bromobenzyl sulfide to
Benzyl 4-bromobenzyl sulfone using H2O2 in
the presence of zirconium tetrachloride ........ 286
Conclusion ............................................ 287
References ............................................ 287
9.3. WO3-30% H2O2-cinchona alkaloids: a new
heterogeneous catalytic system for asymmetric
oxidation and kinetic resolution of racemic
sulfoxides ............................................. 288
Vinay V. Thakur and A. Sudalai
9.3.1. Synthesis of (R)-2-[[[3-Methyl-4-(2,2,2-
trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]
-lH-benzimadazole {(R)-(+)-Lansoprazole} ....... 288
9.3.2. Synthesis of (R)-(+)-Phenyl benzyl
sulfoxide ...................................... 290
Conclusion ............................................ 293
References ............................................ 293
9.4. Benzyl-4,6-O-isopropyIidene-α-(D)-glucopyranoside,
2-deoxy-2-[[(2-hydroxy-3,5-di-rerr-butylphenyl)
methylene]amino] as a ligand for vanadium-catalyzed
asymmetric oxidation of sulfides ...................... 293
Raffaella Del Litto, Guiseppina Roviello and
Francesco Ruffo
9.4.1. Synthesis of Benzyl-4,6-0-isopropylidene-α-
D-glucopyranoside, 2-deoxy-2-[[(2-hydroxy-
3,5-di-tert-butylphenyl)methylene]imine] ....... 294
9.4.2. Oxidation of Thioanisole ....................... 295
Conclusion ............................................ 296
References ............................................ 296
9.5. Asymmetric sulfoxidation of aryl methyl sulfides
with hydrogen peroxide in water ....................... 297
Alessando Scarso and Giorgio Strukul
9.5.1. Synthesis of complex (R)-BINAP)PtCl2 ........... 298
9.5.2. Synthesis of complex [((R)-BINAP)Pt(OH))]2
(BF4)2 ......................................... 299
9.5.3. Stereoselective catalytic oxidation of aryl
methyl sulfides ................................ 300
Conclusion ............................................ 300
References ............................................ 301
Index ......................................................... 303
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