Hydrolysis, oxidation and reduction

Catalysts are increasingly used by chemists engaged in fine chemical synthesis within both industry and academia. Today, there exists a huge choice of high-tech catalysts, which add enormously to the repertoire of synthetic possibilities. However, catalysts are occasionally capricious, sometimes difficult to use and almost always require both skill and experience in order to achieve optimal results. This series aims to be a practical help for advanced undergraduate, graduate and postgraduate students, as well as experienced chemists in industry and academia working in organic and organometallic synthesis.
The series features:
* Tested and validated procedures.
* Authoritative reviews on classes of catalysts.
* Assessments of all types of catalysts.
* Expertise from the Leverhulme Centre for Innovative Catalysis, Liverpool, UK.
The review section in the first volume of the series contains a report by Stanley M. Roberts on the integration of biotransformations into the catalyst portfolio.
The procedure section contains a wide variety of synthetic protocols, such as epoxidations of unsaturated ketones and esters, asymmetric reductions of carbon-oxygen double bonds, asymmetric hydrogenations of carbon-carbon double bonds and other types of reaction. The featured catalysts include a wide range of different materials such as poly-D-leucine, D-fructose-based dioxiranes, oxaborolidine borane, some important titanium and ruthenium complexes as well as baker's yeast. For each reaction there are one or several detailed protocols on how to prepare and employ the various catalysts.

Author Notes

Stanley M. Roberts is the editor of Hydrolysis, Oxidation and Reduction, Volume 1, published by Wiley.

Geraldine Poignant is the editor of Hydrolysis, Oxidation and Reduction, Volume 1, published by Wiley.

K. Daikai and M. Kamaura and J. InanagaD.C. Sherrington and J.K. Karjalainen and O.E.O. HormiRui Zhang and Wing-Yiu Yu and Chi-Ming CheP.O'Brien and S.A. Osborne and D.D. ParkerJean-Michel VateleLaura Palombi and Arrigo ScettriKathelyne Everaere and Jean-Francois Carpentier and Andre Mortreux and Michel BulliardT. ImamotoDiego A. Alonso and Pher G. AnderssonMukund P. Sibi and James W. ChristensenChris H. Senanayake and H. Scott Wilkinson and Gerald J. TanouryMukund P. Sibi and Pingrong Liu and Gregory R. CookMichael A. BrookP.H. Dixneuf and C. Bruneau and P. Le GendreVirginie Ratovelomanana-Vidal and Jean-Pierre GenetJahyo Kang and Jun Hee LeeMatthias Lotz and Juan J. Almena Perea and Paul KnochelTakayuki Doi and Takashi Takahashi

Series Preface	p. xiii
Preface to Volume 1	p. xv
Abbreviations	p. xvii
Part I Review	p. 1
1 The Integration of Biotransformations into the Catalyst Portfolio	p. 3
1.1 Hydrolysis of esters, amides, nitriles and oxiranes	p. 4
1.2 Reduction reactions	p. 9
1.2.1 Reduction of carbonyl compounds	p. 10
1.2.2 Reduction of alkenes	p. 13
1.3 Oxidative transformations	p. 17
1.4 Carbon-carbon bond-forming reactions	p. 26
1.5 Conclusions	p. 37
References	p. 39
Part II Procedures	p. 47
2 General Information	p. 49
3 Asymmetric Epoxidation	p. 51
3.1 Introduction	p. 51
References	p. 52
4 Epoxidation of [alpha], [beta]-Unsaturated Carbonyl Compounds	p. 55
4.1 Non-asymmetric epoxidation	p. 55
4.2 Asymmetric epoxidation using poly-d-leucine	p. 56
4.2.1 Synthesis of leucine N-carboxyanhydride	p. 57
4.2.2 Synthesis of immobilized poly-d-leucine	p. 58
4.2.3 Asymmetric epoxidation of (E)-benzylideneacetophenone	p. 59
4.2.4 Conclusion	p. 61
4.3 Asymmetric epoxidation using chiral modified diethylzinc	p. 61
4.3.1 Epoxidation of 2-isobutylidene-1-tetralone	p. 62
4.3.2 Conclusion	p. 64
4.4 Asymmetric epoxidation of (E)-benzylideneacetophenone using the La-(R)-BINOL-Ph[subscript 3]PO/cumene hydroperoxide system	p. 66
4.4.1 Merits of the system	p. 68
References	p. 69
5 Epoxidation of Allylic Alcohols	p. 71
5.1 Non-asymmetric epoxidation	p. 72
5.2 Asymmetric epoxidation using a chiral titanium complex	p. 73
5.2.1 Epoxidation of cinnamyl alcohol	p. 74
5.2.2 Epoxidation of (E)-2-methyl-3-phenyl-2-propenol	p. 76
5.2.3 Epoxidation of (E)-2-hexen-1-ol	p. 78
5.2.4 Conclusion	p. 81
5.3 Asymmetric epoxidation of (E)-undec-2-en-1-ol using poly(octamethylene tartrate)	p. 81
5.3.1 Synthesis of branched poly (octamethylene-L-(+)-tartrate)	p. 81
5.3.2 Asymmetric epoxidation of (E)-undec-2-en-1-ol	p. 82
References	p. 86
6 Epoxidation of Unfunctionalized Alkenes and [alpha], [beta]-Unsaturated Esters	p. 87
6.1 Asymmetric epoxidation of disubstituted Z-alkenes using a chiral salen-manganese complex	p. 88
6.1.1 Epoxidation of (Z)-methyl styrene	p. 89
6.1.2 Epoxidation of (Z)-ethyl cinnamate	p. 91
6.1.3 Conclusion	p. 93
6.2 Asymmetric epoxidation of disubstituted E-alkanes using a D-fructose based catalyst	p. 94
6.2.1 Epoxidation of (E)-stilbene	p. 95
6.2.2 Conclusion	p. 97
6.3 Enantioselective epoxidation of (E)-[beta]-methylstyrene by D[subscript 2]-symmetric chiral trans-dioxoruthenium (VI) porphyrins	p. 98
6.3.1 Preparation of the trans-dioxoruthenium (VI) complexes with D[subscript 2]-symmetric porphyrins (H[subscript 2]L[superscript 1-3])	p. 98
6.3.2 Enantioselective epoxidation of (E)-[beta]-methylstyrene	p. 99
6.3.3 Conclusion	p. 100
References	p. 101
7 Asymmetric Hydroxylation and Aminohydroxylation	p. 103
7.1 Asymmetric aminohydroxylation of 4-methoxystyrene	p. 103
7.1.1 Conclusion	p. 105
7.2 Asymmetric dihydroxylation of (1-cyclohexenyl)acetonitrile	p. 105
7.2.1 (R,R)-(1,2-Dihydroxycyclohexyl)acetonitrile acetonide	p. 107
7.2.2 Conclusion	p. 108
References	p. 108
8 Asymmetric Sulfoxidation	p. 109
8.1 Asymmetric oxidation of sulfides and kinetic resolution of sulfoxides	p. 109
8.1.1 Asymmetric oxidation of 4-bromothioanisole	p. 109
8.1.2 Kinetic resolution of racemic 4-bromophenyl methyl sulfoxide	p. 111
References	p. 113
9 Asymmetric Reduction of Ketones Using Organometallic Catalysts	p. 115
9.1 Introduction	p. 115
9.2 Asymmetric hydrogenation using a metal catalyst: [Ru((S)-BiNAP)]	p. 117
9.3 Asymmetric transfer hydrogenation of [beta]-ketoesters	p. 121
9.4 (S,S)-1,2-bis(tert-Butylmethylphosphino)ethane (BisP*): Synthesis and use as a ligand	p. 123
9.4.1 Synthesis of BisP*	p. 123
9.4.2 Synthesis of 1,2-bis(tert-butylmethylphosphino) ethaneruthenium bromide (BisP*-Ru)	p. 125
9.4.3 Synthesis of (R)-(-)-methyl 3-hydroxypentanoate using (BisP*-Ru)	p. 126
9.5 (1S,3R,4R)-2-Azanorbornylmethanol, an efficient ligand for ruthenium-catalysed asymmetric transfer hydrogenation of aromatic ketones	p. 127
9.5.1 Synthesis of ethyl(1S,3R,4R)-2-[(S)-1-phenylethylamino]-2-azabicyclo[2.2.1] hept-5-ene-3-carboxylate	p. 129
9.5.2 Synthesis of (1S,3R,4R)-3-hydroxymethyl-2-azabicyclo[2.2.1]heptane	p. 131
9.5.3 Ruthenium-catalysed asymmetric transfer hydrogenation of acetophenone	p. 133
References	p. 134
10 Asymmetric Reduction of Ketones Using Bakers' Yeast	p. 137
10.1 Bakers' yeast reduction of ethyl acetoacetate	p. 137
10.2 Enantioselective synthesis of cis-N-carbobenzyloxy-3-hydroxyproline ethyl ester	p. 140
10.2.1 Immobilization of bakers' yeast	p. 140
10.2.2 Bakers' yeast reduction of cis-N-carbobenzyloxy-3-ketoproline ethyl ester	p. 140
References	p. 142
11 Asymmetric Reduction of Ketones Using Nonmetallic Catalysts	p. 143
11.1 Introduction	p. 143
11.2 Oxazaborolidine borane reduction of acetophenone	p. 146
11.3 Oxazaphosphinamide borane reduction of chloroacetophenone	p. 148
11.4 Asymmetric reduction of chloroacetophenone using a sulfoximine catalyst	p. 151
11.4.1 Preparation of [beta]-hydroxysulfoximine borane	p. 151
11.4.2 Reduction of chloroacetophenone using the sulfoximine borane	p. 153
11.4.3 Summary	p. 155
11.5 Asymmetric reduction of bromoketone catalysed by cis-aminoindanol oxazaborolidine	p. 157
11.5.1 Synthesis of aminoindanol oxazaborolidine	p. 157
11.5.2 Asymmetric reduction of 2-bromo-(3-nitro-4-benzyloxy)acetophenone	p. 157
11.5.3 Conclusions	p. 159
11.5.4 Stereoselective reduction of 2,3-butadione monoxime trityl ether	p. 161
11.5.5 Stereoselective reduction of methyl 3-oxo-2-trityloxyiminostearate	p. 163
11.5.6 Stereoselective reduction of 1-(tert-butyldimethylsilyloxy)-3-oxo-2-trityloxyiminooctadecane	p. 164
11.6 Enantioselective reduction of ketones using N-arylsulfonyl oxazaborolidines	p. 166
11.6.1 Synthesis of N-(2-pyridinesulfonyl)-1-amino-2-indanol	p. 166
11.6.2 Asymmetric reduction of a prochiral ketone (chloroacetophenone)	p. 167
11.7 Reduction of ketones using amino acid anions as catalyst and hydrosilane as oxidant	p. 169
References	p. 172
12 Asymmetric Hydrogenation of Carbon-Carbon Double Bonds Using Organometallic Catalysts	p. 175
12.1 Introduction	p. 176
12.2 Hydrogenation of dimethyl itaconate using [Rh((S,S)-Me-BPE)]	p. 177
12.3 Hydrogenation of an [alpha]-amidoacrylate using [Rh((R,R)-Me-DuPHOS)]	p. 179
12.4 Hydrogenation of an [alpha]-amidoacrylate using [Rh(B[3.2.0]DPO)] complexes	p. 180
12.4.1 Preparation of (COD)[subscript 2] Rh[superscript +]BF[subscript 4 superscript -]	p. 180
12.4.2 Preparation of the bisphosphinite ligand	p. 182
12.4.3 Asymmetric reduction of [alpha]-acetamido cinnamic acid	p. 184
12.5 Hydrogenation of enol carbonates and 4-methylene-N-acyloxazolidinone using [Rh((R)-BiNAP)] complexes	p. 186
12.5.1 Synthesis of (S)-4,4,5-trimethyl-1, 3-dioxolane-2-one	p. 186
12.5.2 Synthesis of (S)-2-methyl-2,3-butanediol	p. 187
12.5.3 Preparation of optically active N-acyloxazolidinones	p. 188
12.5.4 Synthesis of (R)-N-propionyl-4,5,5-trimethyl-1, 3-oxazolidin-2-one	p. 189
12.6 Enantioselective ruthenium-catalyzed hydrogenation of vinylphosphonic acids	p. 190
12.6.1 Synthesis of chiral Ru(II) catalysts	p. 190
12.6.2 Asymmetric hydrogenation of vinylphosphonic acids carrying a phenyl substituent at C[subscript 2]	p. 191
12.6.3 Asymmetric reduction of a vinylphosphonic acid carrying a naphthyl substituent at C[superscript 2]	p. 192
12.6.4 Scope of the hydrogenation reaction	p. 193
12.7 Synthesis of a cylindrically chiral diphosphine and asymmetric hydrogenation of dehydroamino acids	p. 194
12.7.1 Preparation of (R,R)-1,1'-bis([alpha]-hydroxypropyl) ferrocene	p. 195
12.7.2 Preparation of (R,R)-1,1'-bis [alpha-(dimethylamino)propyl]ferrocene	p. 196
12.7.3 Preparation of (R,R,[subscript p]S,[subscript p]S)-1,1'-bis [alpha-(dimethylamino)propyl]-2,2'-bis (diphenyl-phosphino)ferrocene	p. 197
12.7.4 Preparation of (R,R,[subscript p]S,[subscript p]S)-1,1'-bis [alpha-acetoxypropyl)-2,2'-bis(diphenyl-phosphino)ferrocene	p. 198
12.7.5 Preparation of ([subscript p]S,[subscript p]S)-1, 1'-bis (diphenylphosphino)-2,2'-bis(1-ethylpropyl) ferrocene [(S,S)-3-Pt-FerroPHOS]	p. 199
12.7.6 Preparation of [(COD)Rh(([subscript p]S, [subscript p]S)-1, 1'-bis(diphenylphosphino)-2,2'-bis (1-ethylpropyl)ferrocene superscript +]BF[superscript - subscript 4]	p. 200
12.7.7 Asymmetric hydrogenation of [alpha]-acetamido cinnamic acid	p. 201
12.8 Synthesis and application of diamino FERRIPHOS as ligand for enantioselective Rh-catalysed preparation of chiral [alpha]-amino acids	p. 202
12.8.1 Synthesis of 1,1'-di(benzoyl)ferrocene	p. 202
12.8.2 Synthesis of (S,S)-1,1'-bis ([alpha]-hydroxyphenylmethyl)ferrocene	p. 204
12.8.3 Synthesis of (S,S)-1,1'-bis ([alpha]-acetoxyphenylmethyl)ferrocene	p. 205
12.8.4 Synthesis of (S,S)-1,1'-bis([alpha]-N,N-dimethylaminophenylmethyl)ferrocene	p. 206
12.8.5 Synthesis of ([alpha]S, [alpha]'S)-1,1'-bis([alpha]-N, N-dimethylaminophenylmethyl)-(R,R)-1,1'bis(diphenylphosphino)ferrocene	p. 207
12.8.6 Asymmetric hydrogenation of methyl-(Z)-3-phenyl-2-methyl-carboxamido-2-propenoate using (S)-(R)-diamino FERRIPHOS as chiral ligand	p. 209
References	p. 210
13 Employment of Catalysts Working in Tandem	p. 213
13.1 A one-pot sequential asymmetric hydrogenation utilizing Rh(I)- and Ru(II)-catalysts	p. 213
13.1.1 Synthesis of ethyl (Z)-4-acetamido-3-oxo-5-phenyl-4-pentenoate	p. 213
13.1.2 Asymmetric hydrogenation of ethyl 4-acetamido-3-oxo-5-phenyl-4-pentenoate	p. 214
References	p. 217
Index	p. 219

Available:*

On Order

Summary

Summary

Author Notes

Table of Contents