Читать книгу Enzyme-Based Organic Synthesis - Cheanyeh Cheng - Страница 4

1 Chapter 1Scheme 1.1 The primary structure of a polypeptide chain linked by the peptid...Scheme 1.2 The proposed enzyme reaction mechanism by Michaelis and Menten.Scheme 1.3 A generalized enzyme‐catalyzed reaction.Figure 1.1 The number of binding sites of a substrate with enzyme determines...Figure 1.2 Three‐point attachment rule shows that only one enantiomer of the...Figure 1.3 The stereospecificity of enzyme for two substrate enantiomers by ...Scheme 1.4 Enantioselective synthesis of (3aS,6aR)‐lactone.Scheme 1.5 The enantioselective conversion of HPMAE to (S)‐phenylephrine....Scheme 1.6 Regio‐ and stereoselective concurrent oxidations of racemic vicin...

2 Chapter 2Scheme 2.1 Oxidation of benzyl alcohol using an oxidase and a catalase.Scheme 2.2 Oxidation of benzyl alcohol via alcohol dehydrogenases or microbi...Scheme 2.3 Regio‐ and stereoselective concurrent oxidations of (±)‐1,2 diols...Scheme 2.4 Deracemization of racemic 1‐phenyl‐1,2‐ethanediol by C. parapsilo...Scheme 2.5 Biocatalytic racemization of sec‐alcohols and acyloins using lyop...Scheme 2.6 Oxidation of an alcohol intermediate to the precursor of atranori...Scheme 2.7 Bioconversion of isoeugenol to vanillin and vanillic acid by N. i...Figure 2.1 Hydroxylation of alkanes by cytochrome P450 monooxygenase (CYP)....Scheme 2.8 Terminal hydroxylation of long‐chain alkanes by LadA.Scheme 2.9 Hydroxylation of alkanes by fungal peroxygenase.Scheme 2.10 The catalytic hydroxylation of L‐phenylalanine and L-tyrosine by...Scheme 2.11 Hydroxylation of naringenin in the culture of the recombinant S....Scheme 2.12 Hydroxylation of isoliquiritigenin in human liver by cytochrome ...Scheme 2.13 Hydroxylation of d‐amphetamine by cytochrome P450 to give p‐hydr...Scheme 2.14 Catabolic pathways of monosubstituted benzene to diol via cis‐di...Scheme 2.15 Chemoenzymatic preparation of pancratistatin analogs.Scheme 2.16 Whole‐cell fermentation of methyl 2‐iodobenzoate for organic syn...Scheme 2.17 Toluene dioxygenase catalyzed cis‐dihydroxylation of phenols tow...Scheme 2.18 Naphthalene dioxygenase catalyzed cis‐dihydroxylation of naphtha...Scheme 2.19 Regioselective oxidation of biphenyl by the Rhodococcus sp. DK17...Scheme 2.20 Postulated reaction mechanism for the formation of thymol from pScheme 2.21 The epoxidation reaction catalyzed by squalene epoxidase (SE).Scheme 2.22 The synthesis of enantiopure 2‐amino‐1‐phenyl and 2‐amino‐2‐phen...Scheme 2.23 Epoxidation of ally phenyl ether for producing chiral phenyl gly...Scheme 2.24 Stereoselective epoxidation of unsaturated bicyclic γ‐lactones....Scheme 2.25 Synthesis of optically pure S‐sulfoxide by co‐expressed E. coli....Scheme 2.26 The multiple enzyme biosynthesis of ω‐hydroxyundec‐9‐enoic acid ...Scheme 2.27 The Baeyer–Villiger oxidation of cyclohexanone to ε‐caprolactone...Scheme 2.28 Enantiopure asymmetric microbial Baeyer–Villiger oxidation of ra...Scheme 2.29 Enantioselective 2‐hydroperoxylation of saturated and unsaturate...Scheme 2.30 Peroxidation of linoleic acid with soybean lipoxygenase and subs...Scheme 2.31 Mn‐LO mediated peroxidation of linoleic acid.Scheme 2.32 Kinetic resolution of aryl hydroperoxides by HRP.Scheme 2.33 Enantioselectivities of the selenosubtilisin‐catalyzed kinetic r...Scheme 2.34 Asymmetric reduction of ketone precursor o‐chloroacetophenone wi...Figure 2.2 Structure of aprepitant.Scheme 2.35 The asymmetric synthesis of 3,5‐bis(trifluoromethyl) acetophenon...Scheme 2.36 Bioreduction of α‐haloketones in aqueous medium using different ...Scheme 2.37 E. coli or S. cerevisiae catalyzed reduction of bicycle[2.2.2]oc...Scheme 2.38 Yeast mediated enantioselective reduction of ethyl benzoylacetat...Scheme 2.39 Asymmetric reduction of ketones and polymerization of the optica...Scheme 2.40 Asymmetric reduction of activated alkene substrates catalyzed by...Scheme 2.41 Asymmetric reduction of α‐methylmaleic acid dimethylester with Z...Scheme 2.42 Asymmetric bioreduction of citraconic acid dimethylester via a c...Scheme 2.43 BY fermentations and OYEs 1–3 mediated bioreductions of substrat...Scheme 2.44 The reduction of γ,δ‐double bond of the conjugated lactone in se...

3 Chapter 3Scheme 3.1 The transamination between acetophenone and excessive isopropyl a...Scheme 3.2 Enzyme cascade reactions for the conversion of L‐threonine to L‐h...Scheme 3.3 The formation of N‐benzylacetamide from benzaldehyde through an e...Scheme 3.4 The enzymatic cascade route toward all four diastereomers of 4‐am...Scheme 3.5 The oxidation/transamination cascade reactions for the biosynthes...Scheme 3.6 Synthesis of sitagliptin from prositagliptin ketone using immobil...Scheme 3.7 Galactosyltransferase catalyzed glycosylation with UDP‐2‐d‐Gal as...Scheme 3.8 Method for avoiding product inhibition in GalT‐catalyzed glycosyl...Scheme 3.9 β‐1,4‐GalT catalyzed galactosylation of natural glycosides and co...Scheme 3.10 Two‐step synthesis of glycogen with glycogenin functioning as an...Scheme 3.11 The transfer of γ‐phosphoryl group from ATP to hydroxyl group co...Scheme 3.12 Phosphorylation of 4HT to 4PHT by kinase DUF1537 for enzyme cofa...Scheme 3.13 Sequential phosphorylation of peptide R‐SSD3 with casein kinases...Scheme 3.14 Synthetic pathway of melatonin from serotonin by two kinds of ac...Scheme 3.15 Protein acetylation with CRTase and DAMC without involving acety...

4 Chapter 4Scheme 4.1 Esterase activity with heterotrophic bacteria isolated from neutr...Scheme 4.2 FRET‐based PLE catalyzed ester hydrolysis.Scheme 4.3 cis‐2‐(2‐Methyl‐acryloyloxy‐methyl)‐cyclopropanecarboxylic acid e...Scheme 4.4 PLE catalyzed hydrolysis of chrysanthemic acid esters: (a) cis/tr...Scheme 4.5 Kinetic resolution of racemic ester for producing chiral TA with ...Scheme 4.6 Esterase‐catalyzed kinetic resolution of racemic IPG esters.Scheme 4.7 Enantioselective hydrolysis of dimethyl 2‐methyl‐2‐phenylmalonate...Scheme 4.8 Esterase‐catalyzed enantioselective hydrolysis of 2‐cyano cyclopr...Scheme 4.9 Lipases‐catalyzed hydrolysis of triacylglycerols.Scheme 4.10 Enantioselective hydrolysis of (±)‐1,2‐diacetoxy‐3‐chloropropane...Scheme 4.11 BCL‐catalyzed kinetic resolution of β‐substituted‐γ‐acetyloxymet...Scheme 4.12 Candida antarctica lipase B‐catalyzed asymmetric alcoholysis of ...Scheme 4.13 CPL‐catalyzed kinetic resolution of BPA alkyl esters (a–e) with ...Scheme 4.14 Kinetic resolution of water‐insoluble α‐acyloxy esters with immo...Scheme 4.15 Lipase‐mediated biodiesel oil production using ionic liquids as ...Scheme 4.16 Protease‐catalyzed desymmetrization to form Valganciclovir hydro...Scheme 4.17 Tandem enzymatic resolution of racemic α‐aminoalkanedioic acid d...Scheme 4.18 Protease‐catalyzed degradation of TRH in blood, organs, and brai...Scheme 4.19 Enantioselective hydrolysis of racemic naproxen amide with R. er...Scheme 4.20 Whole cell catalyzed enantioselective biotransformations of race...Scheme 4.21 Enzymatic hydrolysis pathways for nitrile to form carboxylic aci...Scheme 4.22 Phosphatases‐catalyzed hydrolysis of a phosphate ester bond.Scheme 4.23 Coupled enzymes synthesis of L‐fructose from rac‐glyceraldehyde ...Scheme 4.24 T6PP catalyzed hydrolysis of T6P for trehalose biosynthesis.Scheme 4.25 Kinetic resolution of racemic nitro‐substituted phenoxypropylene...Scheme 4.26 The enantioselectivity of epoxide hydrolases from two different ...Scheme 4.27 Enantioselective hydrolysis of racemic 3‐chlorostyrene oxide to ...Scheme 4.28 Kinetic resolution of racemic epichlorohydrin for producing (R)‐...Scheme 4.29 Enantioconvergent processes for 2‐, 3‐, or 4‐pyridyloxirane by t...Scheme 4.30 Kinetic resolution of glycidate ester with immobilized crude ext...Scheme 4.31 Hydrolysis of DL‐5‐monosubstituted hydantoins for optically pure...Scheme 4.32 Production of N‐carbamoyl‐D‐phe derivatives using D‐hydantoinase...Scheme 4.33 Enantiospecific hydrolysis of fluorinated rac‐5‐arylhydantoins w...Scheme 4.34 Enantioselective synthesis of L‐homophenylalanine by hydantoinas...Scheme 4.35 The route of hydantoinase catalyzed hydrolysis of racemic 6‐subs...Figure 4.1 (a) Linear polymer of amylose molecule with α‐D‐1,4‐glycosidic bo...Figure 4.2 (a) Molecular structure of cellulose with β‐1,4‐glycosidic linkag...Scheme 4.36 Integrated enzyme cascade‐chemocatalytic cellulose conversion in...Scheme 4.37 Acetone‐butanol‐ethanol (ABE) produced from rice straw via ethan...Figure 4.3 Structure of xylan with different side chains attached.

5 Chapter 5Scheme 5.1 Stereochemical complementary sets of DHAP‐dependent aldolases....Scheme 5.2 FSA‐catalyzed self‐aldol addition using glycoaldehyde as the dono...Scheme 5.3 N‐Acetylneuraminic acid (NeuAc) aldolase‐catalyzed aldol reaction...Scheme 5.4 KDPG mutant aldolase accepting nonphosphorylated and altered subs...Scheme 5.5 Aldol reactions catalyzed by acetaldehyde‐dependent DERA. In comp...Scheme 5.6 Sequential aldol reaction catalyzed by DERA with acetaldehyde as ...Scheme 5.7 Application DERA mutant S238D catalyzed sequential on‐pot reactio...Scheme 5.8 Stereocomplementary aldol reactions with glycine‐dependent ThrAs....Scheme 5.9 Synthetic application of glycine‐dependent ThrA.Scheme 5.10 PDC‐catalyzed synthesis of (R)‐PAC and its use for the productio...Scheme 5.11 Direct asymmetric synthesis of meta‐ and para‐substituted (S)‐be...Scheme 5.12 Benzoylformate decarboxylase‐mediated asymmetric acyloin condens...Scheme 5.13 General reaction scheme for BAL‐catalyzed carboligations.Scheme 5.14 Diastereoselective condensation of benzaldehyde and racemic (±)‐...Scheme 5.15 (a) BAL‐catalyzed 2,3‐dioxygenated aryl propanones. Source: Base...Scheme 5.16 Acyloin condensation of phenylacetic acid with PhDC.Scheme 5.17 HNL‐catalyzed enantioselective cyanohydrin formation.Scheme 5.18 HNL‐catalyzed enantioselective synthesis of cyanohydrins from al...Scheme 5.19 HNL‐catalyzed enantioselective synthesis of cyanohydrins from ar...Scheme 5.20 HNL‐catalyzed cyanohydrin formation from 2‐, 3‐, 4‐monosubstitut...Scheme 5.21 HNL‐catalyzed production of chiral unsaturated cyanohydrins as i...Scheme 5.22 Chemoenzymatic synthesis of (R)‐pantolactone for vitamin B₅ prod...Scheme 5.23 (R)‐HNL‐catalyzed synthesis of (R)‐4‐methylsulfanyl‐mandelonitri...Scheme 5.24 (a) Electrophilic water addition to isolated C=C bonds following...Scheme 5.25 Hydration of oleic acid by OAH yielding (R)‐hydroxystearic acid....Scheme 5.26 A two‐step process with the combination of oleate hydratase from...Scheme 5.27 Multistep enzymatic cascade synthesis of α,ω‐dicarboxylic acid, ...Scheme 5.28 Linalool dehydratase‐isomerase catalyzed transformation of (S)‐l...Scheme 5.29 Limonene hydratase catalyzed addition of water to (R)‐(+)‐limone...Scheme 5.30 Fumarase‐catalyzed hydration of fumarate to form (S)‐malate.Scheme 5.31 Fumarase‐catalyzed synthesis of l‐threo‐chloromaleic acid and it...Scheme 5.32 Malease‐catalyzed water addition of maleic acid to form (R)‐mali...Scheme 5.33 ECH1‐ and ECH2‐catalyzed water addition to trans‐2‐enoyl‐CoA thi...Scheme 5.34 Aspartate ammonia lyase catalyzed reversible deamination reactio...Scheme 5.35 Industrial synthesis of artificial sweetener aspartame with the ...Scheme 5.36 Multienzymatic cascade synthesis of l‐phenylalanine from phenylp...Scheme 5.37 Multienzymatic cascade reaction for the production of β‐alanine ...Scheme 5.38 Synthesis of N‐substituted aspartic acid derivatives with aspart...Scheme 5.39 Synthesis of enantiopure (R)‐3‐aminobutyric acid with mutant asp...Scheme 5.40 3‐Methylasparte ammonia lyase catalyzes the reversible deaminati...Scheme 5.41 Synthesis of aspartic acid derivatives with wild‐type CtMAL.Scheme 5.42 Engineered MAL variants catalyzed amination with broad nucleophi...Scheme 5.43 Aromatic amino acid ammonia‐lyases catalyzed reversible deaminat...Scheme 5.44 RgPAL‐catalyzed amination for the synthesis of substituted pheny...Scheme 5.45 RgPAL‐catalyzed biphasic amination for l‐phenylalanine methyl es...Scheme 5.46 PAL‐catalyzed deamination of nonaromatic cyclic phenylalanine an...Scheme 5.47 Synthesis of l‐propargylglycine by PcPAL immobilized on MNPs in ...Scheme 5.48 Preparation of d‐AADs by kinetic resolution of racemic AADs.Scheme 5.49 Kinetic resolution of rac‐histidine using HAL for simultaneous s...Scheme 5.50 Synthesis of substituted d‐phenylalanines from corresponding cin...Scheme 5.51 Synthesis of (S)‐β‐arylalanines by the direct amination of aryla...Scheme 5.52 Kinetic resolution of racemic β‐phenylalanines using coupled PAM...Scheme 5.53 Kinetic resolution of racemic β‐phenylalanines using coupled Enc...Scheme 5.54 Three‐step one‐pot chemoenzymatic synthesis of enantiopure aryal...Scheme 5.55 Two‐step one‐pot chemoenzymatic synthesis of l‐aryalanines from ...Scheme 5.56 RgPAL‐mediated chemoenzymatic cascade synthesis of (S)‐2‐indolin...Scheme 5.57 Multienzymatic cascade synthesis for substituted para‐vinylpheno...Scheme 5.58 PAL/TAL‐mediated in vivo biosynthesis of various secondary metab...Scheme 5.59 γ‐Cleavage of l‐cystathionine catalyzed by cystathionine γ‐lyase...Scheme 5.60 β‐elimination reaction with cystathionine β‐lyase to produce cor...Scheme 5.61 β‐elimination of S‐alkyl‐l‐cysteine sulfoxides with alliin lyase...Scheme 5.62 l‐Methionine degradation catalyzed by methione γ‐lyase to yield ...Scheme 5.63 Two aerobic biosynthetic pathways for ergothioneine.Scheme 5.64 Proposed biosynthetic pathway for ovothiol A.Scheme 5.65 The dehalogenation of a vicinal halohydrin by halohydrin dehalog...Scheme 5.66 Synthesis of chiral epoxides by HHDH: (a) DehA‐catalyzed reactio...Scheme 5.67 DKR process of aromatic chlorohydrins catalyzed by HHDH for prod...Scheme 5.68 HheA10‐catalyzed kinetic resolution of racemic aromatic halohydr...Scheme 5.69 HHDH‐catalyzed 1,2‐epoxybutane ring opening for yielding various...Scheme 5.70 Enantioselective epoxide ring‐opening reactions catalyzed by Hhe...Scheme 5.71 HHDH‐catalyzed synthesis of atorvastatin side‐chain precursor et...Scheme 5.72 HHDH‐catalyzed one‐pot tandem enantioselective epoxide ring open...Scheme 5.73 HHDH‐catalyzed regio‐ and enantioselective azidolysis of spiroep...Scheme 5.74 HheC‐catalyzed nitrite‐mediated ring opening of p‐nitrostyrene o...Scheme 5.75 HHDH‐catalyzed epoxide ring opening with cyanate for chiral oxaz...Scheme 5.76 Multienzymatic cascade synthesis of β‐substituted alcohols by th...Scheme 5.77 One‐pot bienzymatic cascade synthesis of ethyl (R)‐hydroxyglutar...Scheme 5.78 Chemoenzymatic cascade synthesis of (S)‐chromanmethanol toward o...

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 (RScheme 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 SmC...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 (5R)‐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 (2S)‐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 CO₂ fixation 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...

8 Chapter 8Scheme 8.1 Merrifield’s solid‐phase synthesis of a dipeptide; Cbz, benzyloxy...Figure 8.1 Split–mix synthesis library in three cycles and each cycle with t...Scheme 8.2 Removal of the enzyme‐labile urethane protecting group from lipop...Scheme 8.3 Enzymatic cleavage of (a) endo‐ and (b) oxo‐linker to release pro...Figure 8.2 Orthogonality issues in biocatalysis.Scheme 8.4 Significance of orthogonality on the production of analogues usin...Scheme 8.5 Iterative synthesis of a 600‐member library from bergenin in two ...Scheme 8.6 Chemically synthesized combinatorial library of cross‐conjugated ...Scheme 8.7 Chemoenzymatically library synthesis by Ugi four‐component conden...Scheme 8.8 Unnatural oligosaccharide library synthesized by using UDP‐Gal an...Scheme 8.9 Enzymatic synthesis of the glycosylated amino acid derivative bui...Scheme 8.10 (a) Biosynthesis of Csypyrone B1 with mutant CsyB. (b) Combinato...Scheme 8.11 Chemical genetic strategy for discovery new macrolide antibiotic...Scheme 8.12 The precursor‐directed biosynthesis of micacocidin derivatives w...Scheme 8.13 DhbE catalyzed aryl acid activation and the generation of nonnat...Scheme 8.14 Triterpene saponin biosynthesis pathway in engineered yeast.Figure 8.3 Biodegradation pathway for propylene retrieved from the UM‐BBD. (...