Cheanyeh Cheng - Enzyme-Based Organic Synthesis

6 Chapter 6Scheme 6.1 Racemases catalyzed racemization of amino acids.Scheme 6.2 Proline racemase catalyzed interconversion of L‐proline to D‐prol...Scheme 6.3 Diaminopimelate epimerase catalyzed stereoconversion of (L,L)‐2,6...Scheme 6.4 Amino acid racemase catalyzed isomerization of L‐ or D‐threonine ...Scheme 6.5 The production of D‐glutamic acid from L‐glutamic acid by enzymat...Scheme 6.6 Lactate racemase (LarA) catalyzed racemization of D‐ and L‐lactic...Scheme 6.7 Mandelate racemase catalyzed reversible interconversion of the ( R Scheme 6.8 Deracemization of rac ‐mandelate using a stepwise lipase‐mandelate...Scheme 6.9 One‐pot enzymatic cascade production of methyl ( R )‐ o ‐chloromande...Scheme 6.10 One‐pot three‐step enzymatic cascade biotransformation for enant...Scheme 6.11 Enantioconvergent synthesis of ( R )‐mandelic ethyl ester catalyze...Scheme 6.12 Reversible conversion of N ‐acetyl‐D‐glucosamine to N ‐acetyl‐D‐ma...Scheme 6.13 Synthesis of Neu5Ac from GlcNAc with a two‐step enzymatic cascad...Scheme 6.14 Reversible racemization of D‐ and L‐isomers of 5‐monosubstituted...Scheme 6.15 The enzymatic cascade reactions for the total conversion of race...Scheme 6.16 The “double‐racemase hydantoinase process” for optically pure L‐...Scheme 6.17 Hydantoinase process used for the production of D‐phenylglycine ...Scheme 6.18 Maleate isomerase catalyzed isomerization of maleic acid to fuma...Scheme 6.19 Bioconversion of maleic acid into L‐malic acid by consecutive ca...Scheme 6.20 Linoleate isomerase catalyzed isomerization of cis ‐9, cis ‐12‐oct...Scheme 6.21 The isomerization of either D‐xylose or D‐glucose catalyzed by x...Scheme 6.22 Hydride shift mechanism of xylose (glucose) isomerase.Scheme 6.23 Simultaneous isomerization and fermentation of D‐xylose for etha...Scheme 6.24 Conversion of D‐glucose to D‐psicose by coupling D‐xylose isomer...Scheme 6.25 Integrated enzyme cascade‐chemocatalytic conversion of cellulose...Scheme 6.26 D‐Mannitol production by simultaneous enzymatic isomerization an...Scheme 6.27 L‐Rhamnose isomerase catalyzed reversible isomerization between ...Scheme 6.28 Production of D‐allose from D‐fructose via D‐psicose by using D‐...Scheme 6.29 Production of L‐lyxose from ribitol using sequential microbial a...Scheme 6.30 Two‐step enzymatic synthesis of 6‐deoxy‐L‐psicose from L‐rhamnos...Scheme 6.31 The isomerization reaction of L‐fucose catalyzed by L‐fucose iso...Scheme 6.32 Two‐step enzymatic synthesis of L‐fuculose from L‐fucose.Scheme 6.33 A step‐by‐step coupled enzymatic synthesis of L‐glucose and L‐fr...Scheme 6.34 Enzyme cascade reactions for the synthesis of L‐fucose analogs....Scheme 6.35 Structures of L‐fucose and L‐fucose analogs modified at chain te...Scheme 6.36 Phosphopentomutase catalyzed reversible transfer of a phosphate ...Scheme 6.37 Biosynthesis of adenosine from ribose 5‐phosphate by immobilized...Scheme 6.38 Isomerization of D‐xylose 1‐phosphate into D‐xylulose 5‐phosphat...Scheme 6.39 Enzymatic synthesis of 2’‐deoxyinosine from glucose, acetaldehyd...Scheme 6.40 One‐pot multistep enzymatic synthesis of thymidine 5’‐diphosphat...Scheme 6.41 Lysine 2,3‐aminomutase catalyzes the interconversion of L‐lysine...Scheme 6.42 Chemical structures of tuberactinamine A, tuberactinomycin A, an...Scheme 6.43 Pathway of N ε‐acetyl‐β‐lysine synthesis in methanogenic arc...Scheme 6.44 Stereochemical reactions catalyzed by lysine 5,6‐aminomutase....Scheme 6.45 Reaction of racemic lysine catalyzed by lysine 2,3‐aminomutase a...Scheme 6.46 Tyrosine 2,3‐aminomutase catalyzed isomerization of L‐tyrosine t...Scheme 6.47 Biosynthetic pathway for the β‐amino acid moiety of the C‐1027 e...Scheme 6.48 Biosynthetic pathway for the synthesis of chondramides from L‐ty...Scheme 6.49 Biosynthesis of ( R )‐β‐dopa in C. violaceous with L‐tyrosine as p...Scheme 6.50 Phenylalanine aminomutase from Taxus chinensis catalyzed L‐α‐phe...Scheme 6.51 Dynamic kinetic resolution of racemic α‐phenylalanine to yield (Scheme 6.52 Kinetic resolution of racemic β‐phenylalanine and its derivative...Scheme 6.53 Conversion of α‐phenylalanine to β‐phenylalanine catalyzed by PA...Scheme 6.54 Isomerization of L‐phenylalanine to ( S )‐β‐phenylalanine catalyze...Scheme 6.55 Isomerization of L‐phenylalanine catalyzed by PAM from P. fluore ...Scheme 6.56 Whole‐cell biocatalyst catalyzed substituted α‐phenylalanines to...Scheme 6.57 L‐Phenylalanine to ( S )‐β‐phenylalanine catalyzed by the enzyme A...Scheme 6.58 PAM HitA catalyzed conversion of L‐phenylalanine to ( S )‐β‐phenyl...Scheme 6.59 Cyclization of all‐ trans geranylgeranyl diphosphate to ent ‐copal...Scheme 6.60 Conversion from geranylgeranyl diphosphate to ent ‐kaurene cataly...Scheme 6.61 Biosynthetic pathways in S. miltiorrhiza for gibberellins produc...Scheme 6.62 Miltiradiene production from GGPP catalyzed by the fusion of Sm C...Scheme 6.63 Triptolide production catalyzed by Tripterygium wilfordii .Scheme 6.64 The biosynthesis of defense‐related dolabralexins in maize.Scheme 6.65 Lycopene β‐cyclase catalyzed conversion of lycopene to β‐caroten...Scheme 6.66 Carotenoid biosynthetic pathway in higher plants.Scheme 6.67 Biosynthesis of isorenieratene form β‐carotene via β‐isorenierat...Scheme 6.68 Biosynthetic pathway of carotene and xanthophyll in Capsicum .Scheme 6.69 Biosynthetic pathway in P. tricornutum from β‐carotene to diadin...

7 Chapter 7Scheme 7.1 ATP‐dependent olefin β‐lactone synthetase catalyzed β‐lactone for...Scheme 7.2 Proposed reaction mechanism for the formation of β‐lactone from β...Scheme 7.3 β‐Lactones formation from β‐hydroxy acids catalyzed by ATP‐depend...Scheme 7.4 Formation of acetyl‐CoA from acetate, ATP, and CoA catalyzed by a...Scheme 7.5 Two‐step reaction for the conversion of acetate into acetyl‐CoA c...Scheme 7.6 Coupled‐enzymatic reactions for citric acid production from oxalo...Scheme 7.7 In vitro biosynthesis of poly(3‐hydroxybutyric acid) using cascad...Scheme 7.8 Simplified metabolic pathways for fatty acids biosynthesis from a...Scheme 7.9 MACS‐catalyzed two‐step reaction of medium‐chain carboxylate to f...Scheme 7.10 Glycine conjugation of carboxylic acids catalyzed by MACS and GL...Scheme 7.11 Biosynthetic pathway for mcl‐PHAs synthesis from 2‐alkenoic acid...Scheme 7.12 SCL‐ co ‐MCL copolymer production using engineered E. coli with in...Scheme 7.13 Enantioselective thioesterification of racemic CPPA catalyzed by...Scheme 7.14 (a) Production of butylmalonyl‐CoA from ( E )‐2‐hexenoyl‐CoA catal...Scheme 7.15 Biosynthesis of novel terminal‐alkyne‐bearing polyketide startin...Scheme 7.16 Pathways of JA biosynthesis in plant peroxisomes.Scheme 7.17 (a) Schematic pathway for the conversion of sucrose to triacylgl...Scheme 7.18 Acyl‐CoA‐dependent or –independent TAG synthesis pathway derived...Scheme 7.19 The de novo TAG biosynthesis pathway constructed by modification...Scheme 7.20 Condensation of glutamate and ammonia to generate glutamine cata...Scheme 7.21 Two primary pathways for glutamate synthesis in E. coli .Scheme 7.22 Biosynthetic pathway of nitrogen assimilation into glutamine, as...Scheme 7.23 Theanine production by coupling the reaction of GS with glucose ...Scheme 7.24 Biosynthesis of the antibiotic bacilysin from L-alanine and the ...Scheme 7.25 Hypothesized biosynthetic pathway from prephenate to bacilysin....Scheme 7.26 Enzymatic production of 2‐amino‐ N ‐(2‐furylmethyl)propanamide (AF...Scheme 7.27 ATP‐dependent formation of carbapenam‐3‐carboxylate catalyzed by...Scheme 7.28 Biosynthetic pathway of (5 R )‐carbapen‐2‐em‐3‐carboxylic acid cat...Scheme 7.29 CarA catalyzed conversion of three different stereoisomers of 5‐...Scheme 7.30 Conversion of disubstituted‐5‐CMP derivatives into disubstituted...Scheme 7.31 Pyruvate carboxylase catalyzed MgATP‐dependent carboxylation of ...Scheme 7.32 Glucose metabolism in E. coli expressed with R. etli PYC. (a) Ae...Scheme 7.33 Central anaerobic metabolic pathway of mutant E. coli SBS110MG b...Scheme 7.34 Anaerobic mixed acid fermentation pathway for E. coli . (a) Coexp...Scheme 7.35 Predominant anaerobic metabolic pathways of C. glutamicum for su...Scheme 7.36 Metabolically engineered S. cerevisiae employed for succinate pr...Scheme 7.37 Major metabolic pathways for the production of malate in T. glab ...Scheme 7.38 PMA biosynthesis based on comparative metabolome analysis.Scheme 7.39 Major metabolic pathways lead to the formation of fumarate I in Scheme 7.40 Proposed metabolic pathways of propionic acid fermentation with ...Scheme 7.41 Biosynthetic pathway toward 3‐hydroxypropionic acid from glucose...Scheme 7.42 Biosynthetic pathway of L-lysine via the d,L-diaminopimelate int...Scheme 7.43 Lysine and biotin production using PYC and biotin protein ligase...Scheme 7.44 Acetyl‐CoA carboxylase catalyzed carboxylation of acetyl‐CoA to ...Scheme 7.45 Type II fatty acid synthetic pathway. The ACC is a heterotetrame...Scheme 7.46 Fatty acid metabolic pathway of engineered E. coli . Overexpressi...Scheme 7.47 Engineered E. coli for free monounsaturated fatty acid productio...Scheme 7.48 Simplified principal metabolic pathways for lipid synthesis in Y ...Scheme 7.49 Proposed mechanism of SCD‐mediated deregulation of fatty acid pa...Scheme 7.50 Lipid metabolism of engineered S. cerevisiae for fatty alcohol p...Scheme 7.51 Engineered E. coli for production of phloroglucinol from glucose...Scheme 7.52 Metabolically engineered S. argillaceus for production of mithra...Scheme 7.53 Metabolic pathways of engineered Y. lipolytica for TAAL synthesi...Scheme 7.54 Engineered ethanol‐driven biosynthetic system for production of ...Scheme 7.55 Biosynthesis of (2 S )‐flavanones by engineered E. coli .Scheme 7.56 Engineering central metabolic pathways in E. coli for plant flav...Scheme 7.57 Engineered E. coli for biosynthesis of 7‐OMA starting from p ‐cou...Scheme 7.58 Biosynthesis of 5‐deoxyflavanones in engineered E. coli .Scheme 7.59 Engineered E. coli for biosynthesis of 4‐hydroxycoumarin, naring...Scheme 7.60 Metabolically engineered S. cerevisiae for high kaempferol produ...Scheme 7.61 Modular strategy to optimize biosynthetic pathways in S. cerevis ...Scheme 7.62 3‐Hydroxypropionic acid production from glucose through malonyl‐...Scheme 7.63 Proposed 3‐HP cycle of autotrophic CO 2fixation in the phototrop...Scheme 7.64 Biosynthetic pathway of 3‐HP in engineered Synechocystis .Scheme 7.65 Engineered S. elongatus with a balanced driving force module for...Scheme 7.66 3‐HP biosynthetic pathway in engineered S. cerevisiae . Bold arro...