Catalytic Synthesis of Fine Chemicals: Hydrolysis, Oxidation, and Reduction

Author: [British] S.M. Roberts G. Pauwels
Publisher:
Publish Date: 2005-05-01
Features: This book is divided into two parts. The first part describes certain natural and non-natural catalysts used in asymmetric hydrolysis, oxidation, reduction, and carbon-carbon bond formation reactions in fine chemical synthesis. The second part describes the new laboratory applications of catalysts for asymmetric oxidation and reduction reactions, with most experimental reports primarily focusing on non-natural catalysts. This book is suitable as a reference book for senior undergraduate and graduate students, researchers, and engineering and technical personnel engaged in fine organic synthesis.
Table of Contents
Abbreviations
Glossary
Part 1: Review
1. A Review of Biocatalytic Methods in the Field of Catalysts
1.1 Hydrolysis of Esters, Amides, Nitriles, and Ethylene Oxide Derivatives
1.2 Reduction Reactions
1.2.1 Reduction of Carbonyl Compounds
1.2.2 Reduction of Alkenes
1.3 Oxidation Transformations
1.4 Carbon-Carbon Bond Formation Reactions
1.5 Conclusion
References
Part 2: Experimental Methods
2. A Review of Asymmetric Epoxidation
3. Asymmetric Epoxidation of α,β-Unsaturated Carbonyl Compounds
3.1 Non-Asymmetric Epoxidation
3.2 Asymmetric Epoxidation Catalyzed by Poly-D-Leucine
3.2.1 Synthesis of Leucine N-Carboxylate Anhydride
3.2.2 Synthesis of Immobilized Poly-D-Leucine
3.2.3 Asymmetric Epoxidation of (E)-Styryl Phenyl Ketone
3.2.4 Conclusion
3.3 Asymmetric Epoxidation Catalyzed by Chiral Modified Diethyl Zinc
3.3.1 Epoxidation of 2-(2′-Methyl-1′-allyl)-1-tetralone
3.3.2 Conclusion
3.4 Asymmetric Epoxidation of (E)-Styryl Phenyl Ketone Using La-(R)-BINOL-Ph3PO/Isopropylphenyl Hydroperoxide
References
4. Epoxidation of Allyl Alcohol
4.1 Non-Asymmetric Epoxidation
4.2 Asymmetric Epoxidation Catalyzed by Chiral Titanium Complexes
4.2.1 Epoxidation of 3-Phenyl-2-propen-1-ol
4.2.2 Epoxidation of (E)-2-Methyl-3-phenyl-2-propen-1-ol
4.2.3 Epoxidation of (E)-2-Hexen-1-ol
4.2.4 Conclusion
4.3 Asymmetric Epoxidation of (E)-Undec-2-ene-1-ol Using Poly(Tartaric Acid Dimethylene Ester)
4.3.1 Synthesis of Branched-Chain Poly(L-()-Tartaric Acid Dimethylene Ester)
4.3.2 Asymmetric Epoxidation of (E)-Undec-2-ene-1-ol
References
5. Epoxidation of Non-Functionalized Alkenes and α,β-Unsaturated Esters
5.1 Asymmetric Epoxidation of Disubstituted Z-Alkenes Using Chiral Salen-Mn Complex Catalysts
5.1.1 Epoxidation of (Z)-1-Methyl-2-phenyl Ethene
5.1.2 Epoxidation of (Z)-3-Phenyl-2-propenoic Acid Ethyl Ester
5.1.3 Conclusion
5.2 Asymmetric Epoxidation of Disubstituted (E)-Alkenes Using D-Fructose-Based Catalysts
5.2.1 Epoxidation of (E)-1,2-Diphenyl Ethene
5.2.2 Conclusion
5.3 Asymmetric Epoxidation of (E)-1-Methyl-2-phenyl Ethene Using D2-Symmetric Chiral Trans-dioxoruthenium(VI) Porphyrin Catalysts
5.3.1 Preparation of D2-Symmetric Porphyrin (H2L1～3) for Trans-dioxoruthenium(VI) Complexes
5.3.2 Asymmetric Epoxidation of (E)-1-Methyl-2-phenyl Ethene
5.3.3 Conclusion
References
6. Asymmetric Hydroxylation and Asymmetric Amino Hydroxylation
6.1 Asymmetric Amino Hydroxylation of 4-Methoxy Styrene
6.2 Asymmetric Dihydroxylation of (1-Cyclohexenyl) Acetonitrile
6.2.1 Preparation of (R,R)-(1,2-Dihydroxycyclohexyl) Acetonitrile-Acetone Dehydration Compound
6.2.2 Conclusion
References
7. Asymmetric Sulfonation Oxidation
7.1 Asymmetric Oxidation of Sulfides and Kinetic Resolution of Sulfites
7.2 Kinetic Resolution of Racemic 4-Bromophenyl Methyl Sulfite
References
8. Asymmetric Hydrogenation Reduction of Ketones Using Organometallic Catalysts
8.1 Introduction
8.2 Asymmetric Hydrogenation of Ketones Using Metal Catalysts [Ru((S)-BiNAP)]
8.3 Asymmetric Transfer Hydrogenation of β-Keto Esters
8.4 (S,S)-1,2-Bis(tert-butylmethylphosphino) Ethane (BisP): Synthesis and Use as a Ligand
8.4.1 Synthesis of BisP
8.4.2 Synthesis of 1,2-Bis(tert-butylmethylphosphino) Ethane Dibromoruthenium (BisP - Ru)
8.4.3 Synthesis of (R)-(-)-3-Hydroxyvaleric Acid Methyl Ester Using (BisP - Ru)
8.5 (1S,3R,4R)-2-Norbornyl Methanol: An Efficient Ligand for Asymmetric Transfer Hydrogenation of Aromatic Ketones Using Ruthenium Catalysts
8.5.1 Synthesis of (1S,3R,4R)-2-[(S)-1-Phenethylamino]-2-Norbornanone-3-carboxylic Acid Ethyl Ester
8.5.2 Synthesis of (1S,3R,4R)-3-Hydroxymethyl-2-Norbornanone
8.5.3 Ruthenium-Catalyzed Asymmetric Transfer Hydrogenation of Methyl Phenyl Ketone
References
9. Bread Yeast for Asymmetric Reduction of Ketones
9.1 Bread Yeast for Reduction of Ethyl Acetoacetate
9.2 Enantioselective Synthesis of (Z)-N-Benzyloxy Carbonyl-3-Carbonyl Proline Ethyl Ester
9.2.1 Immobilization of Bread Yeast
9.2.2 Reduction of (Z)-N-Benzyloxy Carbonyl-3-Carbonyl Proline Ethyl Ester Using Bread Yeast
References
10. Non-Metallic Catalysts for Asymmetric Reduction of Ketones
10.1 Introduction
10.2 Reduction of Methyl Phenyl Ketone Using Borazarole-Borane Complexes
10.3 Reduction of Chloromethyl Phenyl Ketone Using Phosphonaziridinyl-Borane Complexes
10.4 Asymmetric Reduction of Chloromethyl Phenyl Ketone Using Imidinosulfone Catalysts
10.4.1 Preparation of β-Hydroxyiminosulfone
10.4.2 Reduction of Chloromethyl Phenyl Ketone Using Imidinosulfone-Borane Complexes
10.4.3 Summary
10.5 cis-1-Amino-2,3-dihydro-2-indanol Borazarole for Asymmetric Reduction of Brominated Ketones
10.5.1 Synthesis of 1-Amino-2,3-dihydro-2-indanol Borazarole
10.5.2 Asymmetric Reduction of Bromomethyl-(3′-Nitro-4′-benzyloxy)phenyl Ketone
10.5.3 Conclusion
10.5.4 Stereoselective Reduction of 2,3-Butanedione Monoxime Triphenyl Methyl Ether
10.5.5 Stereoselective Reduction of 3-Oxo-2-triphenylmethyloxoimino Stearic Acid Methyl Ester
10.5.6 Stereoselective Reduction of 1-(Tert-butyl dimethylsilyloxy)-3-oxo-2-triphenylmethyloxoimino Octadecane
10.6 N-Arylsulfonate Borazarole for Enantioselective Reduction of Ketones
10.6.1 Synthesis of N-(2-Pyridinesulfonyl)-1-amino-2,3-dihydro-2-indanol
10.6.2 Asymmetric Reduction of Prochiral Ketones (Chloromethyl Phenyl Ketone)
10.7 Reduction of Ketones Using Amino Acid Anion as Catalyst and Silane as Reducing Agent
References
11. Organometallic Catalysts for Asymmetric Reduction of Carbon-Carbon Double Bonds
11.1 Introduction
11.2 Reduction of Methyl Phenyl Ketone Using [Rh-(S,S)-Me-BPE]
11.3 Reduction of α-Acetamido Acrylic Acid Esters Using [Rh(S,S)-Me-DuPHOS]
11.4 Reduction of α-Acetamido Acrylic Acid Esters Using [Rh(B[3.2.0]DPO)] Complexes
11.4.1 Preparation of (COD)2RhBF-4
11.4.2 Preparation of Secondary Phosphine Ligands
11.4.3 Asymmetric Reduction of α-Acetamido-3-phenyl-2-propenoic Acid
11.5 Reduction of Carbonate Enol Esters and 4-Methylene-N-Acyl-Oxazolidinones Using [Rh-(R)-BiNAP] Complexes
11.5.1 Synthesis of (S)-4,4,5-Trimethyl-1,3-dioxolane-2-one
11.5.2 Synthesis of (S)-2-Methyl-2,3-butanediol
11.5.3 Synthesis of Optically Active N-Acyl Oxazolidinones
11.5.4 Synthesis of (R)-N-Propanoyl-4,5,5-trimethyl-1,3-oxazolidin-2-one
11.6 Enantioselective Rhodium Catalytic Hydrogenation of Vinyl Phosphonates
11.6.1 Synthesis of Chiral Ru(Ⅱ) Catalysts
11.6.2 Asymmetric Hydrogenation of Vinyl Phosphonates with Aromatic Substitution at the C2 Position
11.6.3 Asymmetric Hydrogenation of Vinyl Phosphonates with Naphthalene Substitution at the C2 Position
11.6.4 Scope of Hydrogenation Reactions
11.7 Synthesis and Dehydrogenation of Cylindrical Chiral Diphosphines and Asymmetric Hydrogenation of Dehydrogenated Amino Acids
11.7.1 Preparation of (R,R)-1,1′-Di(α-hydroxypropyl) Ferrocene
11.7.2 Preparation of (R,R)-1,1′-Bis[α-(dimethylamino)propyl] Ferrocene
11.7.3 Preparation of (R,R,pS,pS)-1,1′-Di[α-(dimethylamino)propyl]-2,2′-Bis(diphenylphosphino) Ferrocene
11.7.4 Preparation of (R,R,pS,pS)-1,1′-Di(α-acetoxypropyl)-2,2′-Bis(diphenylphosphino) Ferrocene
11.7.5 (pS,pS)-1,1′-Di(diphenylphosphino)-2,2′-Di(1-ethylpropyl) Ferrocene [(S,S)-3-Pt-Fe(Ⅱ)-PHOS]
11.7.6 Preparation of [(COD)Rh(pS,pS)-1,1′-Di(diphenylphosphino)-2,2′-Di(1-ethylpropyl) Ferrocene] BF-4
11.7.7 Asymmetric Hydrogenation of α-Acetamido-3-phenyl-2-propenoic Acid
11.8 Synthesis and Use of DiaminoFerriPHOS as a Ligand for Enantioselective Rhodium Catalysts for the Preparation of Chiral α-Amino Acids
11.8.1 Synthesis of 1,1′-Dibenzoyl Ferrocene
11.8.2 Synthesis of (S,S)-1,1′-Di(α-hydroxyphenylmethyl) Ferrocene
11.8.3 Synthesis of (S,S)-1,1′-Di(α-acetoxyphenylmethyl) Ferrocene
11.8.4 Synthesis of (S,S)-1,1′-Di(α-N,N-dimethylaminophenylmethyl) Ferrocene
11.8.5 (αS,α′S)-1,1′-Di(α-N,N-dimethylaminophenylmethyl)-(R,R)-1,1′-Di(diphenylphosphino) Ferrocene
11.8.6 Asymmetric Hydrogenation of (Z)-3-Phenyl-α-acetamido-2-propenoic Acid Methyl Ester Using (S)-((R)-DiaminoFerriPHOS) as a Chiral Ligand
References
12. Applications of Catalysts in Tandem Reactions
12.1 Tandem Asymmetric Hydrogenation Using Rh(Ⅰ)- and Ru(Ⅱ)-Catalysts
12.2 Synthesis of (Z)-4-Acetamino-3-oxo-5-phenyl-4-penten
12.3 Asymmetric Hydrogenation of (Z)-4-Acetamino-3-oxo-5-phenyl-4-penten
References