Multi-Step Enzyme Catalysis Biotransformations and Chemoenzymatic Synthesis

by Garcia-Junceda, Eduardo

• ISBN13: 9783527319213
• ISBN10: 3527319212
• Edition: 1st
• Format: Hardcover
• Copyright: 2008-10-20
• Publisher: Wiley-VCH

Summary

The first comprehensive coverage of this unique and interdisciplinary field provides a complete overview, covering such topics as chemoenzymatic synthesis, microbial production of DNA building blocks, asymmetric transformations by coupled enzymes and much more. By combining enzymatic and synthetic organic steps, the use of multi-enzyme complexes and other techniques opens the door to reactions hitherto unknown, making this monograph of great interest to biochemists, organic chemists, and chemists working with/on organometallics, as well as catalytic chemists, biotechnologists, and those working in the pharmaceutical and fine chemical industries.

Author Biography

Eduardo Garc+¡a-Junceda received his PhD at the Plant Physiology Department at the University of Madrid. He joined Chi-Huey Wong's Group at The Scripps Research Institute (La Jolla, California) as postdoctoral fellow. After his return to Spain in 1995, he was appointed Research Staff Member in the Institute of Organic Chemistry of CSIC in 1997. His research interests concentrate on molecular biology applied to organic synthesis and enzyme catalysis.

Table of Contents

Preface	p. XI
Lise of Contributors	p. XIII
Asymmetric Transformations by Coupled Enzyme and Metal Catalysis: Dynamic Kinetic Resolution	p. 1
Introduction	p. 1
Some Fundamentals for DKR	p. 2
Enzymes for Kinetic Resolution	p. 2
Metal Catalysts for Racemization	p. 3
Enzyme-Metal Combination for DKR	p. 5
(R)- and (S)-Selective DKR	p. 5
Examples of DKR	p. 6
First DKR of Secondary Alcohols	p. 6
DKR of Secondary Alcohols with Racemization Catalyst 1	p. 6
DKR of Secondary Alcohols with Racemization Catalyst 2	p. 8
DKR of Secondary Alcohols with Racemization Catalyst 3	p. 9
DKR of Secondary Alcohols with Racemization Catalyst 4	p. 10
DKR of Secondary Alcohols with Racemization Catalyst 5	p. 10
DKR of Secondary Alcohols with Racemization Catalyst 6	p. 11
DKR of Secondary Alcohols with Racemization Catalyst 7	p. 12
DKR of Secondary Alcohols with Air-Stable Racemization Catalysts	p. 13
DKR of Secondary Alcohols with Racemization Catalyst 10	p. 14
DKR of Secondary Alcohols with Aluminum Catalysts	p. 14
DKR of Secondary Alcohols with Vanadium Catalysts	p. 15
Conclusions	p. 16
References	p. 17
Chemoenzymatic Routes to Enantiomerically Pure Amino Acids and Amines	p. 21
Introduction	p. 21
Amino Acids	p. 23
Amines	p. 33
References	p. 38
Oxidizing Enzymes in Multi-Step Biotransformation Processes	p. 41
Oxidizing Enzymes in Biocatalysis	p. 41
Classes of Oxidizing Enzymes	p. 41
Mechanisms of Biological Oxidation and Implications for Multi-Enzyme Biocatalysis	p. 44
Multi-Step Biotransformation Processes Involving Oxidation	p. 45
Design and Development of New Multi-Enzyme Oxidizing Processes	p. 48
Coupling Redox Enzymes	p. 48
Cofactor Recycle in Multi-Step Oxidizing Biocatalytic Systems	p. 51
Examples of Multi-Enzyme Biotransformation Processes Involving Oxidizing Enzymes	p. 52
Coupling of Oxidases with Non-Redox Enzymes	p. 53
Biocatalytic Systems Involving Coupled Oxidizing Enzymes	p. 53
Multi-Enzyme Systems in Whole-Cell Biotransformations and Expression of Redox Systems in Recombinant Hosts	p. 55
Other Applications of Multi-Enzyme Oxidizing Systems	p. 56
Conclusions	p. 58
References	p. 58
Dihydroxyacetone Phosphate-Dependent Aldolases in the Core of Multi-Step Processes	p. 61
Introduction	p. 61
DHAP-Dependent Aldolases	p. 63
Problem of DHAP Dependence	p. 63
DHAP-Dependent Aldolases in the Core of Aza Sugar Synthesis	p. 68
Combined Use of Aldolases and Isomerases for the Synthesis of Natural and Unnatural Sugars	p. 71
DHAP-Dependent Aldolases in the Synthesis of Natural Products	p. 73
Fructose-6-Phosphate Aldolase: An Alternative to DHAP-Dependent Aldolases?	p. 76
Conclusions	p. 78
References	p. 79
Multi-Enzyme Systems for the Synthesis of Glycoconjugates	p. 83
Introduction	p. 83
In Vitro and In Vivo Multi-Enzymes Systems	p. 85
Combinatorial Biocatalysis	p. 86
Synthesis and In Situ Regeneration of Nucleotide Sugars	p. 88
Synthesis of Oligosaccharides, Glycopeptides and Glycolipids Oligosaccharides	p. 94
Combinatorial Biosynthesis	p. 97
Synthesis of Oligosaccharides with Metabolically Engineered Cells	p. 98
Conclusions	p. 102
References	p. 102
Enzyme-Catalyzed Cascade Reactions	p. 109
Introduction	p. 109
Enzyme Immobilization	p. 110
Reaction Types: General Considerations	p. 111
Chiral Alcohols	p. 112
Chiral Amines	p. 114
Chiral Carboxylic Acid Derivatives	p. 121
C-C Bond Formation: Aldolases	p. 127
Oxidations with O[subscript 2] and H[subscript 2]O[subscript 2]	p. 130
Conclusions and Prospects	p. 131
References	p. 132
Multi-modular Synthases as Tools of the Synthetic Chemist	p. 137
Introduction	p. 137
Excised Domains for Chemical Transformations	p. 139
Function of Individual Domains and Domain Autonomy	p. 139
Heterocyclization and Aromatization	p. 139
Macrocyclization	p. 144
Halogenation	p. 147
Glycosylation	p. 150
Methyltransferases	p. 151
Oxidation	p. 153
Conclusions	p. 155
References	p. 156
Modifying the Glycosylation Pattern in Actinomycetes by Combinatorial Biosynthesis	p. 159
Bioactive Natural Products in Actinomycetes	p. 159
Deoxy Sugar Biosynthesis and Gene Clusters	p. 161
Characterization of Sugar Biosynthesis Enzymes	p. 161
Strategies for the Generation of Novel Glycosylated Derivatives	p. 165
Gene Inactivation	p. 165
Gene Expression	p. 166
Combining Gene Inactivation and Gene Expression	p. 166
Endowing a Host with the Capability of Synthesizing Different Sugars	p. 166
Generation of Glycosylated Derivatives of Bioactive Compounds	p. 166
Macrolides	p. 167
Aureolic Acid Group	p. 175
Angucyclines	p. 181
Anthracyclines	p. 186
Indolocarbazoles	p. 191
Aminocoumarins	p. 193
References	p. 194
Microbial Production of DNA Building Blocks	p. 199
Introduction	p. 199
Screening of Acetaldehyde-Tolerant Deoxyriboaldolase and Its Application for DR5P Synthesis	p. 200
Construction of Deoxyriboaldolase-Overexpressing E. coli and Metabolic Analysis of the E. coli Transformants for DR5P Production from Glucose and Acetaldehyde	p. 201
Efficient Production of DR5P from Glucose and Acetaldehyde by Coupling of the Alcoholic Fermentation System of Baker's Yeast and Deoxyriboaldolase-Expressing E. coli	p. 203
Biochemical Retrosynthesis of 2'-Deoxyribonucleosides from Glucose Acetaldehyde and a Nucleobase: Three-Step Multi-Enzyme-Catalyzed Synthesis	p. 204
One-Pot Multi-Step Enzymatic Synthesis of 2'-Deoxyribonucleoside from Glucose, Acetaldehyde and a Nucleobase	p. 206
Improvement of the One-Pot Multi-Step Enzymatic Process for Practical Production of 2'-Deoxyribonucleoside from Glucose, Acetaldehyde and a Nucleobase	p. 207
Conclusions	p. 208
References	p. 210
Combination of Biocatalysis and Chemical Catalysis for the Preparation of Pharmaceuticals Through Multi-Step Syntheses	p. 213
Introduction: Biocatalysis and Chemical Catalysis	p. 213
Pharmaceuticals with Hydrolases	p. 214
Enzymatic Hydrolysis	p. 214
Enzymatic Transesterification	p. 219
Enzymatic Aminolysis	p. 222
Pharmaceuticals with Oxidoreductases	p. 226
Pharmaceuticals with Lyases	p. 227
Conclusions	p. 230
References	p. 231
Index	p. 235
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