Catalysts For Fine Chemical V, Vol. 5 Book

Series Preface     xvii
Preface to Volume 5     xix
Abbreviations     xxi
Industrial Catalysts for Regio- or Stereo-Selective Oxidations and Reductions A Review of Key Technologies and Targets   John Whittall     1
Introduction     2
Reduction of Carbon-Carbon Double Bonds     3
Privileged structures: [alpha]-amino acids and itaconic acids     4
[beta]-Amino acids     5
[alpha]-Alkyl substituted acids     6
[alpha]-Alkoxy substituted acids     8
Unsaturated nitriles     9
Alkenes and allyl alcohols     10
[alpha],[beta]-Unsaturated aldehyde reduction     10
Ketone and Imine Reduction     12
Catalytic hydrogenation of ketones and imines     12
Asymmetric transfer hydrogenation (ATH) catalysts     15
Modified borane reagents     20
Biocatalysts (alcohol dehydrogenases and ketoreductases)     21
Oxidation     23
Sharpless chiral epoxidation of allyl alcohols     23
Dioxirane catalyzed epoxidation     23
Amines and iminium salts     25
Phase transfer catalysts     25
The Julia-Colonna method (polyleucine oxidation)     26
Organocatalytic [alpha]-hydroxylation of ketones     27
Baeyer-Villiger oxidation     27
Chiral sulfoxides     28
References     29
Asymmetric Hydrogenation of Alkenes, Enones, Ene-Esters and Ene-Acids     35
(S)-2,2[prime]-Bis{lcub}[di(4-methoxyphenyl)phosphinyl]oxy{rcub}-5,5[prime],6,6[prime],7,7[prime],8,8[prime]-octahydro-1,1[prime]-binaphthyl as a ligand for rhodium-catalyzed asymmetric hydrogenation   Ildiko Gergely   Csaba Hegedus   Jozsef Bakos     36
Synthesis of (S)-5,5[prime],6,6[prime],7,7[prime],8,8[prime]-Octahydro-1,1[prime]-bi-2-naphthol     37
Synthesis of (S)-2,2[prime]-Bis{lcub}[di(4-methoxyphenyl)phosphinyl]oxy{rcub}-5,5[prime],6,6[prime],7,7[prime],8,8[prime]-octahydro-1,1[prime]-binaphthyl     38
Asymmetric hydrogenation of Dimethyl itaconate     40
Conclusion     41
References     41
Synthesis and application of phosphinite oxazoline iridium complexes for the asymmetric hydrogenation of alkenes   Frederik Menges   Andreas Pfaltz     42
Synthesis of (4S,5S)-2-(5-Methyl-2-phenyl-4,5-dihydro-oxazol-4-yl)-1,3-diphenyl-propan-2-ol     42
Synthesis of (4S,5S)-O-[1-Benzyl-1-(5-methyl-2-phenyl-4,5-dihydro-oxazol-4-yl)-2-phenyl-ethyl]-diphenylphosphinite     43
Synthesis of (4S,5S)-[([eta superscript 4]-1,5-Cyclooctadiene)-{lcub}2-(2-phenyl-5-methyl-4,5-dihydro-oxazol-4-yl)-1,3-diphenyl-2-diphenylphosphinite-propane{rcub}iridium(I)]-tetrakis[3,5-bis(trifluoromethyl)phenyl]borate     45
Asymmetric hydrogenation of trans-[alpha]-Methylstilbene     46
Conclusion     47
References     48
Synthesis and application of heterocyclic phosphine oxazoline (HetPHOX) iridium complexes for the asymmetric hydrogenation of alkenes   Frederik Menges   Pier Giorgio Cozzi     48
Synthesis of (4S)-tert-Butyl-2-(thiophene-2-yl)-4,5-dihydrooxazole     49
Synthesis of (4S)-tert-Butyl-2-(3-diphenylphosphino-thiophene-2-yl)-4,5-dihydrooxazole     50
Synthesis of (4S)-[([eta superscript 4]-1,5-Cyclooctadiene)-{lcub}4-tert-butyl-2-(3-diphenylphosphino-thiophene-2-yl)-4,5-dihydrooxazole{rcub}iridium(I)]-tetrakis [3,5-bis(trifluoromethyl)phenyl]borate     52
Asymmetric hydrogenation of trans-[alpha]-Methylstilbene     53
Conclusion     54
References     54
(R)-2,2[prime],6,6[prime]-Tetramethoxy-bis[di(3,5-dimethylphenyl)phosphino]-3,3[prime]-bipyridine [(R)-Xyl-P-Phos] as a ligand for rhodium-catalyzed asymmetric hydrogenation of [alpha]-dehydroamino acids   Jing Wu   Albert S.C. Chan     55
Synthesis of 3-Bromo-2,6-dimethoxypyridine     55
Synthesis of Bis(3,5-dimethylphenyl)phosphine chloride      56
Synthesis of 3-Bromo-2,6-dimethoxy-4-di(3,5-dimethylphenyl)phosphinopyridine     57
Synthesis of 3-Bromo-2,6-dimethoxy-4-di(3,5-dimethylphenyl)phosphinopyridine     59
2,2[prime],6,6[prime]-Tetramethoxy-bis[di(3,5-dimethylphenyl)phosphinoyl]-3,3[prime]-bipyridine     60
Optical resolution of ([plus or minus])-6 with (-) or (+)-2,3-0,0[prime]-Dibenzoyltartaric acid monohydrate [(R)-6 or (S)-6)]     61
(R)-2,2[prime],6,6[prime]-Tetramethoxy-bis[di(3,5-dimethylphenyl)phosphino]-3,3[prime]-bipyridine [(R)-Xyl-P-Phos, (R)-1]     62
Preparation of the stock solution of [Rh(R-Xyl-P-Phos)(COD)]BF[subscript 4]     63
A typical procedure for the asymmetric hydrogenation of methyl (Z)-2-Acetamidocinnamate     64
References     65
(R,R)-2,3-Bis(tert-butylmethylphosphino)quinoxaline (QuinoXP) as a ligand for rhodium-catalyzed asymmetric hydrogenation of prochiral amino acid and amine derivatives   Tsuneo Imamoto   Aya Koide     55
Synthesis of (R)-tert-Butyl(hydroxymethyl)methylphosphine-borane     66
Synthesis of (R)-Benzoyloxy(tert-butyl)methylphosphine-borane     67
Synthesis of (S)-tert-Butylmethylphosphine-borane     69
(R,R)-2,3-Bis(tert-butylmethylphosphino)quinoxaline (QuinoxP)     70
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
Rhodium-catalyzed asymmetric hydrogenation of indoles   Ryoichi Kuwano   Masaya Sawamura     73
Synthesis of (R)-2-[(S)-1-(Dimethylamino)ethyl]-1-iodoferrocene     73
Synthesis of (R)-2-[(S)-1-(Diphenylphosphinyl)ethyl]-1-iodoferrocene     75
Synthesis of (R,R)-2,2[prime]-Bis[(S)-1-(diphenylphosphinyl)ethyl]-1,1[Prime]-biferrocene     78
Synthesis of (R,R)-2,2[Prime]-Bis[(S)-1-(diphenylphosphino)ethyl]-1,1[Prime]-biferrocene [abbreviated to (S,S)-(R,R)-PhTRAP]     80
Catalytic asymmetric hydrogenation of N-Acetyl-2-butylindole     82
Catalytic asymmetric hydrogenation of 3-Methyl-N-(p-toluenesulfonyl)indole     84
Conclusion     85
References     86
Asymmetric Reduction of Ketones     87
(R,R)-Bis(diphenylphosphino)-1,3-diphenylpropane as a versatile ligand for enantioselective hydrogenations   Natalia Dubrovina   Armin Borner     89
Synthesis of (S,S)-1,3-Diphenylpropane-1,3-diol     89
Synthesis of (S,S)-Methanesulfonyloxy-1,3-diphenylpropane-1,3-diol     91
Synthesis of (R,R)-Bis(diphenylphosphino)-1,3-diphenylpropane     91
Conclusion      93
References     93
Synthesis of both enantiomers of 1-Phenylethanol by reduction of acetophenone with Geotrichum candidum IFO 5767   Kaoru Nakamura   Mikio Fujii   Yoshiteru Ida     93
Cultivation of G. candidum IFO 5767     94
Synthesis of (S)-1-Phenylethanol     95
Synthesis of (R)-1-Phenylethanol     95
Conclusion     97
References     97
Titanocene-catalyzed reduction of ketones in the presence of water. A convenient procedure for the synthesis of alcohols via free-radical chemistry   Antonio Rosales   Juan M. Cuerva   J. Enrique Oltra     97
Titanocene-catalyzed reduction of Acetophenone in the presence of water     98
Titanocene-catalyzed synthesis of Methyl 4-deuterio-4-phenyl-4-hydroxybutanoate     99
References     100
Xyl-tetraPHEMP: a highly efficient biaryl ligand in the [diphosphine RuCl[subscript 2] diamine]-catalyzed hydrogenation of simple aromatic ketones   Paul H. Moran   Julian P. Henschke   Antonio Zanotti-Gerosa   Ian C. Lennon     101
Synthesis of Tri(3,5-dimethylphenyl)phosphine oxide     102
Synthesis of Bis(3,5-dimethylphenyl)-(2-iodo-3,5-dimethylphenyl)phosphine oxide     103
Synthesis of rac-4,4[prime],6,6[prime]-Tetramethyl-2,2[prime]-bis[bis(3,5-dimethylphenyl)phosphinoyl]-biphenyl     105
Synthesis of rac-4,4[prime],6,6[prime]-Tetramethyl-2,2[prime]-bis[bis(3,5-dimethylphenyl)phosphino]-biphenyl [abbreviated to (rac)-Xyl-tetraPHEMP]     106
Synthesis of [(R)-N,N-Dimethyl(1-methyl)benzylaminato-C[superscript 2],N]-{lcub}rac-4,4[prime],6,6[prime]-tetramethyl-2,2[prime]-bis[bis(3,5-dimethylphenyl)phosphino]-biphenyl{rcub}-palladium(II) tetrafluoroborate and separation of the diastereomers     107
Synthesis of (S)-4,4[prime],6,6[prime]-Tetramethyl-2,2[prime]-bis[bis(3,5-dimethylphenyl)phosphino]-biphenyl: [abbreviated to (S)-Xyl-tetraPHEMP) and (R)-4,4[prime],6,6[prime]-Tetramethyl-2,2[prime]-bis[bis(3,5-dimethylphenyl)phosphino]-biphenyl [abbreviated to (R)-Xyl-tetraPHEMP]     108
Synthesis of [(R)-Xyl-tetraPHEMP RuCl[subscript 2] (R,R)-DPEN] and [(S)-Xyl-tetraPHEMP RuCl[subscript 2] (S,S)-DPEN]     110
Reduction of Acetophenone using [(S)-Xyl-tetraPHEMP RuCl[subscript 2] (S,S)-DPEN] as a precatalyst     111
Conclusion     112
References     112
N-Arenesulfonyl- and N-Alkylsulfamoyl-1,2-diphenylethylenediamine ligands for ruthenium-catalyzed asymmetric transfer hydrogenation of activated ketones   Michel (Massoud S.) Stephan   Barbara Mohar     113
Synthesis of N-Arenesulfonyl-1,2-diphenylethylenediamines     113
Preparation of Ru(II)-N-arenesulfonyl-1,2-diphenylethylenediamine complexes     114
Asymmetric transfer hydrogenation of Ethyl benzoylacetate     115
Conclusion     116
References     116
The synthesis and application of BrXuPHOS: a novel monodentate phosphorus ligand for the asymmetric hydrogenation of ketones   Martin Wills   Yingjian Xu   Garden Docherty   Gary Woodward     116
Synthesis of (S)-BrXuPHOS     117
Synthesis of (S,S,SS)-BrXuPHOS-Ru-DPEN     119
General procedure of asymmetric hydrogenation of acetophenone     120
Conclusion     121
Acknowledgement     121
References     121
In Situ formation of ligand and catalyst: application in ruthenium-catalyzed enantioselective reduction of ketones   Jenny Wettergren   Hans Adolfsson     121
Synthesis of (S)-3-Fluoro-1-phenylethanol     122
Conclusion     123
References     124
Synphos and Difluorphos as ligands for ruthenium-catalyzed hydrogenation of alkenes and ketones   Severine Jeulin   Virginie Ratovelomanana-Vidal   Jean-Pierre Genet     125
Synthesis of [RuCl((S)-SYNPHOS)(p-cymene)]Cl     125
Synthesis of [RuCl((S)-DIFLUORPHOS)(p-cymene)]Cl     126
Synthesis of [RuI((S)-DIFLUORPHOS)(p-cymene)]I     127
Synthesis of [NH[subscript 2]R[subscript 2]] [(RuCl(PP))[subscript 2]([Mu]-Cl)[subscript 3]] PP = SYNPHOS or DIFLUORPHOS and R = Me or Et     127
Synthesis of [NH[subscript 2]Me[subscript 2]][RuCl-(S)-DIFLUORPHOS][subscript 2][[Mu]-Cl][subscript 3]     128
Synthesis of in situ generated [RuBr[subscript 2]((S)-SYNPHOS)] and [RuBr[subscript 2]((S)-DIFLUORPHOS)]     129
Conclusion     131
References     131
An arene ruthenium complex with polymerizable side chains for the synthesis of immobilized catalysts   Estelle Burri   Silke B. Wendicke   Kay Severin     132
Synthesis of 2-Methyl-cyclohexa-2,5-dienecarboxylic acid 2-(2-methyl-acryloyloxy)-ethyl ester     133
Synthesis of [[eta superscript 6]-(2-Methyl-benzoic acid 2-(2-methyl-acryloyloxy)-ethyl ester)RuCl[subscript 2]][subscript 2]     134
Conclusion     135
References     135
Selective reduction of carbonyl group in [beta], [gamma]-unsaturated [alpha]-alpha-ketoesters by transfer hydrogenation with Ru-(p-cymene) (TsDPEN)   Minjie Guo   Dao Li   Yanhui Sun   Zhaoguo Zhang     135
Synthesis of Di-[Mu]-chloro-bis[chloro([eta superscript 6]-1-isopropyl-4-methyl-benzene)ruthenium(II)     136
Synthesis of ([plus or minus])-Monotosylate-1,2-diphenyl-1,2-ethylenediamine     136
Synthesis of Ru complex Ru(p-cymene)(TsDPEN)     138
Ru-TsDPEN catalyzed transfer hydrogenation reaction of [beta],[gamma]-unsaturated-[alpha]-ketoesters     139
Conclusion     140
References     141
Preparation of polymer-supported Ru-TsDPEN catalysts and their use for the enantioselective synthesis of (S)-fluoxetine   Liting Chai   Yangzhou Li   Quanrui Wang     141
Synthesis of the supported ligand 9     141
Synthesis of ligand 17     148
General procedure for asymmetric transfer hydrogenation     150
Preparation of (S)-Fluoxetine hydrochloride     151
Conclusion     154
References     154
Polymer-supported chiral sulfonamide-catalyzed reduction of [beta]-keto nitriles: a practical synthesis of (R)-Fluoxetine   Guang-yin Wang   Gang Zhao     155
Synthesis of (R)-3-Amino-1-phenyl-propan-1-ol     155
Synthesis of (R)-ethyl 3-hydroxy-3-phenylpropylcarbamate     156
Synthesis of (R)-3-(Methylamino)-1-phenylpropan-1-ol     157
Synthesis of (R)-Fluoxetine     158
Conclusion     159
References     159
Imine Reduction and Reductive Amination      161
Metal-free reduction of imines: enantioselective Bronsted acid-catalyzed transfer hydrogenation using chiral BINOL-phosphates as catalysts   Magnus Rueping   Erli Sugiono   Cengiz Azap   Thomas Theissmann     162
Synthesis of (R)-2,2[prime]-Bis-methoxymethoxy-[1,1[prime]] binaphthalene (MOM-BINOL)     162
Synthesis of (R)-3,3[prime]-Diiodo-2,2[prime]-bis(methoxymethoxy)-1,1[prime]-binaphthalene     164
Synthesis of 3,3[prime]-Bis-(3,5[prime]-bis-trifluoromethyl-phenyl)-2,2[prime]-bismethoxymethoxy [1,1[prime]-binaphthalene]     165
Synthesis of (R)-3,3[prime]-[3,5-Bis(trifluoromethyl)phenyl]-1,1[prime]-binaphthylphosphate     166
General procedure for the transfer hydrogenation of ketimines     167
Synthesis of [1-(2,4-Dimethyl-phenyl)-ethyl]-(4-methoxy-phenyl)-amine     167
Conclusion     168
References     170
Metal-free Bronsted acid-catalyzed transfer hydrogenation: enantioselective synthesis of tetrahydroquinolines   Magnus Rueping   Thomas Theissmann   Andrey P. Antonchick     170
General procedure for the transfer hydrogenation of quinolines     170
Synthesis of 7-Chloro-4-phenyl-1,2,3,4-tetrahydroquinoline     172
Synthesis of (S)-2-Phenyl-1,2,3,4-tetrahydroquinoline     172
Synthesis of (R)-2-(2-(Benzo[1,3]dioxol-5-yl)ethyl)-1,2.3,4-tetrahydro-quinoline     173
Conclusion     174
References     174
A highly stereoselective synthesis of 3[alpha]-Amino-23,24-bisnor-5[alpha]-cholane via reductive amination   Sharaf Nawaz Khan   Nam Ju Cho   Hong-Seok Kim     175
Synthesis of Tris[(2-ethylhexanoyl)oxy]borohydride     177
Synthesis of 3[alpha]-Acetamino-23,24-bisnor-5[alpha]-cholane     177
Synthesis of 3[alpha]-N-1-[N(3-[4-Aminobutyl])-1,3-diaminopropane]-23,24-bisnor-5[alpha]-cholane     179
Conclusion     181
Acknowledgements     181
References     181
Oxidation of Primary and Secondary Alcohols     183
Copper(Il) catalyzed oxidation of primary alcohols to aldehydes with atmospheric oxygen   Suribabu Jammi   Tharmalingan Punniyamurthy     183
Synthesis of copper(II) complex 1     184
Typical procedure for the oxidation of primary alcohols to aldehydes     185
Conclusion     186
References     187
Solvent-free dehydrogenation of secondary alcohols in the absence of hydrogen abstractors using Robinson's catalyst   G.B.W.L Ligthart   R.H. Meijer   J. v. Buijtenen   J. Meuldijk   J.A.J.M. Vekemans   L.A. Hulshof     187
Dehydrogenation of 2-Octanol using Ru(OCOCF[subscript 3])[subscript 2](CO)(PPh[subscript 3])[subscript 2] as a catalyst     187
Conclusion     188
References     188
2-Iodoxybenzoic acid (IBX)/n-Bu[subscript 4]NBr/CH[subscript 2]Cl[subscript 2]-H[subscript 2]O: a mild system for the selective oxidation of secondary alcohols   Krisada Kittigowittana   Manat Pohmakotr   Vichai Reutrakul   Chutima Kuhakarn     188
Synthesis of 1-Hydroxy-5-decanone     189
Conclusion     192
References     192
Hydroxylation, Epoxidation and Related Reactions     193
Proline-catalyzed [alpha]-aminoxylation of aldehydes and ketones   Yujiro Hayashi   Mitsuru Shoji     194
Synthesis of (R)-2-Anilinoxypropanol     195
Synthesis of (R)-7-Anilinoxy-1,4-dioxaspiro[4.5]decan-8-one     196
Conclusion     197
References     198
Ru/Silia Cat TEMPO-mediated oxidation of alkenes to [alpha]-hydroxyacids   Rosaria Ciriminna   Mario Pagliaro     199
Synthesis of Silia Cat TEMPO     199
Synthesis of 2-(4-Chlorophenyl)-1,2-propanediol     201
Synthesis of 2-(4-Chlorophenyl)-1,2-hydroxypropanoic acid      202
Conclusion     204
References     204
Catalytic enantioselective epoxidation of trans-disubstituted and trisubstituted alkenes with arabinose-derived ulose   Tony K. M. Shing   Gulice Y.C. Leung   To Luk     204
Synthesis of 2[prime],3[prime]-Diisobutyl acetal     205
Synthesis of ulose     206
Asymmetric epoxidation of trans-[alpha]-Methylstilbene using ulose as catalyst at 0 [degree]C     208
Conclusion     209
References     210
VO(acac)[subscript 2]/TBHP catalyzed epoxidation of 2-(2-Alkenyl)phenols. highly regio- and diastereoselective oxidative cyclisation to 2,3-Dihydrobenzofuranols and 3-Chromanols   Alessandra Lattanzi   Arrigo Scettri     211
VO(acac)[subscript 2]/TBHP catalyzed epoxidation of 2-(3,7-Dimethyl-octa-2,6-dienyl)-phenol     212
VO(acac)[subscript 2]/TBHP/TFA catalyzed oxidative cyclization of 2-(3,7-Dimethyl-octa-2,6-dienyl)-phenol     213
Conclusion     214
References     214
An Oxalolidinone ketone catalyst for the asymmetric epoxidation of cis-olefins   David Goeddel   Yian Shi     215
Amadori rearrangement to give 1-Dibenzylamino-1-deoxy-D-fructose     215
Acetal protection of 1-Dibenzylamino-1-deoxy-D-fructose      216
Hydrogenation of the Dibenzylamine     217
Phosgene cyclization of aminoalcohol     218
Alcohol oxidation     220
Synthesis of ketone 2     221
Asymmetric epoxidation of cis-[beta]-Methylstyrene     222
Conclusion     223
References     224
[alpha]-Fluorotropinone immobilised on silica: a new stereoselective heterogeneous catalyst for epoxidation of alkenes with oxone   Giovanni Sartori   Alan Armstrong   Raimondo Maggi   Alessandro Mazzacani   Raffaella Sartorio   France Bigi   Belen Dominguez-Fernandez     225
Synthesis of silica KG-60-supported enantiomerically enriched [alpha]-Fluorotropinone     225
Synthesis of enantiomerically enriched epoxides     226
Conclusion     227
References     228
Asymmetric epoxidation catalyzed by novel azacrown ether-type chiral quaternary ammonium salts under phase-transfer catalytic conditions   Kazushige Hori   Keita Tani   Yasuo Tohda     228
Synthesis of precursor of the azacrown ether     229
Synthesis of the azacrown ether     230
Synthesis of the azacrown ether-type quaternary ammonium salt     232
Asymmetric epoxidation of (E)-Chalcone catalyzed by the azacrown ether-type quaternary ammonium salt as chiral PTC     233
Conclusion     234
References     235
Enantioselective epoxidation of olefins using phase transfer conditions and a chiral [azepinium][TRISPHAT] salt as catalyst   Jerome Vachon   Celine Perollier   Alexandre Martinez   Jerome Lacour     235
Enantioselective epoxidation of 1-Phenyl-3,4-dihydronaphthalene     236
Conclusion     238
References     239
Catalytic asymmetric epoxidation of [alpha],[beta]-unsaturated esters promoted by a Yttrium-biphenyldiol complex   Masakatsu Shibasaki   Hiroyuki Kakei   Shigeki Matsunaga     239
Synthesis of (aS,R)-6,6[prime]-[(Propylene)dioxy]biphenyl-2,2[prime]-diol     240
Synthesis of (aS,R)-2,2-[Oxybis(ethylene)dioxy]-6,6[prime]-[(propylene)dioxy]biphenyl     242
Synthesis of (S)-6,6[prime]-[Oxybis(ethylene)dioxy]biphenyl-2,2[prime]-diol     243
Enantiomeric enrichment of (S)-6,6[prime]-[Oxybis(ethylene)dioxy]biphenyl-2,2[prime]-diol     244
Catalytic asymmetric epoxidation of [alpha],[beta]-unsaturated esters     246
References     248
Catalytic enantioselective epoxidation of [alpha],[beta]-enones with a binol-zinc-complex   Ana Minatti   Karl Heinz Dotz      249
Synthesis of (E)-(2S,3R)-Phenyl-(3-phenyloxiran-2-yl)methanone     249
Conclusion     250
References     251
Asymmetric epoxidation of Phenyl-2-(3[prime]-pyridylvinyl)sulfone using polyleucine hydrogen peroxide gel   Mike R. Pitts   John Whittall     251
Preparation of polyleucine-hydrogen peroxide gel     252
Synthesis of Phenyl-2-(3[prime]-pyridylvinyl) su