457

Index

a S-adenosyl-L-methionine (SAM) 394, 395, acenocoumarol metabolism 104–105 403 O-acetyl α-haloketone formation 445 ADH. See alcohol dehydrogenase N-acetylamino acids 211 adrenodoxin reductase (AdR) 114–115 acetylation 212, 220, 222, 364, 438, 439 agitated tube reactor (ATR) system 204–206 N-acetyl-D-lactosamine (LacNAc) 141, 143, Agrobacterium tumefaciens(Atβcar) 148–152, 378, 379 163, 166, 167, 169–173 N-acetylneuraminate synthase (NeuS) 364, – α, β, γ and δ amino acids 169–171 368, 369, 371, 372, 380 – L-enantiomers and D-antipodes 172–173 N-acetylneuraminic acid (Neu5Ac) 361, 364, – α-methionine and β-alanine 171–173 365, 367–379, 381, 383, 385, 387 α-alanine 161 N-acetyl synthase (NeuS) β-alanine 162 364 L-alanine 446 acrylic fibers 255 AlcalaseⓇ 186–188, 190–192 activity fingerprinting 316 alcohol activity-based protein profiling (ABPP) – amination of 70, 71 404–405 – kinetic resolution of 215–220 acyl compounds racemization 182–183 alcohol dehydrogenase (ADH) 29–31, 34, 45, acylase capillary reactor–microextractor 47, 52, 57, 110–111, 443, 448 system 211 – catalyzed reactions 23, 31, 34, 35 acylase-catalyzed amide hydrolysis 446 – catalyzed reduction 444, 447–449, 451, 452 acylation 202, 212, 213, 218, 219, 431, aldehyde decarbonylase. See 433–434 aldehyde-deformylating (ADO) N-acylation 299 aldehyde dehydrogenase (AldDH) 52, 121, O-acylation 433 414 acyl-transfer 181 aldehyde-deformylating oxygenase (ADO) adenosine triphosphate (ATP) 235, 318, 400, 233 402, 408, 409 aldol reaction 339, 348–350, 353, 382, 449, S-adenosyl-L-methionine (SAM) dependent 451, 452 methyltransferases aldolase-catalyzed reaction 439 – acting on small molecules 398–400 aldoxime dehydratase-nitrile – cascade applications 410–415 hydratase-amidase 255–256 – (re)generation 406–410 aldoxime dehydratases 256 – cofactors 400–403 aliphatic amidase 304 – higher homologs and derivatives 403–406 aliphatic (S)-2-hydroxyamides 261 – radical-SAM enzymes 395–396 aliphatic nitrilases 278–279 – substrates 396–400 alkane degradation 52 N-adenosylaziridine 406 1,ω-alkane diamines 72

Cascade Biocatalysis: Integrating Stereoselective and Environmentally Friendly Reactions, First Edition. Edited by Sergio Riva and Wolf-Dieter Fessner. c 2014 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2014 by Wiley-VCH Verlag GmbH & Co. KGaA. 458 Index

α-alkyl-α-hydroxycarboxylic acids 261 – regeneration, whole-cell biocatalysts aluminum catalyzed racemization 434 114–115 Amberlite XAD-7 207 artificial cascades 257 amberlite-based racemization 438 aryl olefins, biocatalytic asymmetric amidase dihydroxylation 49 – activity and stability, nitrile effect 289–293 arylacetonitrilases 277–278 – cascade substrate selectivity 304–308 L-arylalanines 443 – structure and mechanism 304 asymmetric dihydroxylation, aryl olefins 49 amidase-and nitrile hydratases-catalyzed asymmetric reductive amination 66–69 reaction 286 ATP-binding cassette (ABC) protein 235 amide formation 305 auxiliary agents, enzymes as 317–325 amination 67–69 azetidine-2-carbonitriles 251 – of alcohols 70, 71 azobisisobutyronitrile (AIBN) 435 amine-catalyzed racemization 438 amines 434–436 b – kinetic resolution of 213, 214 bacterial methyltransferases 404 amino acid esters racemization 187 bacterial nitrilases 274 amino acid oxidase (AAO) 233 Baeyer–Villiger (BVMO) amino acid precursors 331–334 27, 45, 46, 52, 53, 56, 57 N-protected-amino acid thioesters 191–192 Baeyer–Villiger oxidation 45, 59, 60 α-amino acids 162, 170–171, 182, 298 β-alanine 172 D α- -amino acids 163 β-alanine synthase. See N-carbamoyl-β-alanine β-amino acids 297–309 amidohydrolase (NCβAA) – production 161–174 β-amino acids δ-amino acids 170–171 – biocatalytic preparation of enantiopure L -amino acids 436 299–301 α-amino esters 436, 437 – chemical methods for generating 298–299 α-amino-α-caprolactam racemase 257 – stereoselective synthesis of 297–309 aminoacylase 299–300 base-catalyzed enolization 183 – cross linked enzyme aggregate (CLEA) of base-catalyzed racemization 180, 183–185, 211 189 amino-and hydroxynitriles 303 β-carbamoylase 166, 173, 174 2-amino-1,3,4-butanetriol 207 benzaldehyde dehydrogenase (BZDH) 52 aminocyclitol synthesis 340–351 benzofurane 441 2-aminoethylphosphonate (2-AEP) 161 3-(oxiran-2yl)benzoic acid 48 β-aminoisobutyric acid 161–162, 166 benzonitrile 252, 253, 263, 285, 289 2-aminonitriles 254 benzyl alcohol dehydrogenase (BADH) 52 β-aminonitriles 254, 306 N-benzyloxycarbonyl (Cbz)-protected aminotransferases 66 aminoaldehyde derivatives 340–341, 349, amminolysis, of N-Boc-aminothioesters 193 350 ammonolysis, of phenylglycine methyl ester biaryl-substituted alcohol 447 186 Bifidobacterium longum UDP- amperometric transketolase assay 323–325 pyrophosphorylase (BLUSP) enzyme 148 CYP19A1 catalysis 94, 96 biocatalyst engineering 153 aromatic nitrilases 278 biomimetic reductive amination process 203 artemisinin-based combination therapies (+)-biotinamidohexanoic acid hydrazide 142 (ACTs) 120 biphasic MTBE/buffer system 190 artificial cascade reactions, cytochrome P450 blood-tolerant laccase 9 enzymes N-Boc-amino acid thioesters hydrolysis 193 – cofactor regenerating enzymes 108–113 N-Boc-aminothioesters 193 – multi-enzyme cascades, in vivo 120–124 N-Boc-phenylglycine thioesters 191 – multi-enzyme cascades, isolated enzymes bovine adrenodoxin (Adx) 114–115 116–120 bovine serum albumin (BSA), 319–325 Index 459

Brevibacterium sp. K1309 (Bs-NOX) enzyme cis-dihydroxylation of benzonitrile 263 33–34 CLEA. See cross-linked enzyme aggregate Burkholderia cepacia lipase 219 CMP-sialic acid synthetase (CSS) 372, BVMO. See Baeyer–Villiger monooxygenase 374–377, 389 coenzyme A (CoA) 161 c coenzyme regeneration enzyme (CRE) 46, CaLB. See Candida antarctica lipase B 108 calcium channel blocker 102 cofactor recycling 44–46 camphor oxidation 113 Co-(III) nitrile hydratases 304 Candida antarctica lipase B (CaLB) 212, 214, combinatorial libraries enhanced by 220, 300, 435 recombination in yeast (CLERY ) 16 Candida rugosa lipase (CrL) 186, 207, 209, compartmentalization 237, 240 210, 213 continuous ideally stirred tank reactor capravirine metabolism 96–98 (CISTR) 200, 201 ε-caprolactone (ε-CL) 445 continuous stirred ultrafiltration carbaldehyde, amination of 77 (UF)-membrane bioreactors (CSMRs) 284, N-carbamoyl-α-methyl-β-alanine 167 285, 287, 289, 290, 292 L-N-α-carbamoylase and D-N-α-carbamoylase continuous-flow enzyme reactors 206 167, 169 continuous-flow kinetic resolution 212, 213, N-carbamoyl-β-alanine amidohydrolase 220 (NCβAA) 162, 163, 166–173 continuous-flow systems N-carbamoyl-β-amino acids 163 – homogeneous vs. heterogeneous 199–200 -active enzyme (CAZy) 134, 377 – micro vs. mini reactors 202 351–355 – reactions in 199–204 carbon–carbon bond formation 80, 259, 319, continuous-flow/stopped-flow (SF) methods 322, 326, 355, 368, 371, 398, 438, 439, 446 203 carbonyl amination 75–78 continuous-stirred tank reactors (CSTRs) 3-carboxymuconate 53 210, 220, 237, 238 catalytic cycle, P450 89–90 convergent synthesis 138, 151–153 catechol-O-methyltransferase (COMT) 398, Coprinopsis cinerea peroxidase (CIP) 12 400 creatinine analysis 203 CAZy. See carbohydrate-active enzyme cross-linked enzyme aggregate (CLEA) 211, cell-free systems (in vitro) 108–113 252 dehydrogenase (CDH) 5 cyanide hydratases 273–275 chemocatalysis 428, 439–442 – properties and applications 277–279 chemo-enzymatic cascade reactions 56–60, cyanide-transforming enzymes 279 133–153, 325–326 (±)-α-cyano-α-fluoro-α-phenylacetic acid chemoenzymatic multistep one-pot processes (CFPA) 253 427–453 1-cyano-2-methoxymethyl ferrocene 255 – chemo process 443–452 cyanopyridine 256, 259 – isomerization and derivatization 429–438 cyclic β-amino acid 438 – isomerization of substrate 428 cyclic malonic acid monoester derivative 449 – substrate synthesis and derivatization cycloalkanones synthesis 117 438–452 trans-1,2-cyclohexanediol acetylation 220 chemoenzymatic synthesis 323, 340, 379 cyclohexanol oxidation 48 chiral amines 65 cytidine 5′-monophosphate sialic acid chiroptical measurements 191–192 synthetase (CSS) 364 1-chloro-2-acetoxy-3-(1-naphthyloxy)-propane cytidine triphosphate (CTP) 372 222 cytochrome P450 enzymes, artificial cascade chlorobenzene dioxygenase (CBDO) 263 reactions cholesterol oxidation 93 – cofactor regenerating enzymes 108–113 ciliatine 161 – multi-enzyme cascades, in vivo 120–124 cinnamyl alcohol 54 – multi-enzyme cascades, isolated enzymes cis-dihydrodiols 262 116–120 460 Index

cytochrome P450 enzymes, artificial cascade e reactions (contd.) ebastine metabolism 103–104 – regeneration, whole-cell biocatalysts enantioselective acylation, of prochiral diols 114–115 212 cytochrome P450 monooxygenases 87–125 enoate reductase 53, 57 cytosine 405 ent-kaurene oxidation 101 enzyme engineering 60, 265, 404 enzyme-mediator systems 35–37 d D--4-phosphate (D-E4P) 318 N-dealkylations 102, 104 ester hydrolysis 436–437, 449 dehydrogenase-catalyzed oxidation reactions ethyl carbamate oxidation 100 23 demethylation, of lanosterol 97 f N-demethylations 106 D-fagomine 349 deoxycorticosterone, oxidation 94 farnesyl pyrophosphate (FPP) 120 deoxysugars 340 FDH. See formate dehydrogenase deracemization 66–67 Fe-(III) nitrile hydratases 304 – of profen thioesters 189 ferredoxin hydrogenase 29 – of racemic amines 78–79 flavin mononucleotide (FMN) cofactor 28 3,5-dichlorosalicylaldehyde-catalyzed flow-through approach, advantages 199 racemization 437 fluidized-bed reactors 201 dihydropyrimidinase 163–166 fluorescent intensity (FLINT) 318 5-dihydrouracils 163 fluorogenic transketolase assay 319–321 dihydrouracils (DHUs), 5-and 5-or 9-fluorophore-labeled sialoconjugates 6-monosubstituted 162, 164, 165 381 (DHA) 330, 346–351, 353, fluoropyruvate 381 355 formate dehydrogenase (FDH) 24–26, dihydroxyacetone phosphate (DHAP) 317, 111–112 320, 322, 340, 341, 343–345, 347 Friedel-Crafts-type alkylation 452 dinitriles 253, 279 D- 6-phosphate (D-F6P) 318 directed molecular evolution 1–3 D-fructose 429, 430 370–371 fructose-6-phosphate aldolase (FSA) 330, 2,6-disubstituted piperidines 75 342, 348–350, 352, 355 DKR. See dynamic kinetic resolution L-fuculose-1-phosphate aldolase (FucA) DL-Ac-Phe, kinetic resolution of 211 341–344, 347, 348 DNA fusion engineering 27 – methylation 393, 394, 400 – methyltransferases 398, 404, 407 g dodecanoic acid methyl ester 55 γ-amino-n-butyric acid (GABA) 161 dopamine methylation 400 ganglioside 144 dTDP-activated deoxysugar synthesis 139 geranylgeranyl pyrophosphate (GGPP) 122 dTDP-deoxy synthesis 141 dehydrogenase (GDH) 24–26 dTDP-2-deoxy-arabino- 139 glucose-6-phosphate dehydrogenase dTDP-deoxyhexoses 139 (G-6P-DH) 29, 108–110 dTDPdeoxysugars 147 – regeneration of NADPH by 30 dTDP-2,6-dideoxyhexoses synthesis 140 glycan microarray technology 388 dynamic kinetic resolution (DKR) 179–194, glycan-binding proteins 388 210, 212, 428–438 glycans 133, 137, 144, 148–151 – of amino acid esters 186 D- 3-phosphate (D-G3P) 317, – of aminoesters 187 318 – applications of 183–193 D-glycerol 3-phosphate 317 –ofN-Boc-phenylglycine thioesters 191 glycerol-3-phosphate dehydrogenase (GPDH) – of oxoesters 185–188 318 – of thioesters 188–193 glycoconjugates 363 Index 461

– synthesis 133–153 hydroxynitrile -nitrilase-amidase 261 (GO) 349, 352–354, 356 hydroxynitrile lyase-nitrile hydratase glycomics 133 261–262 glycosidases 136–137 hydroxynitrile (HnLs) 259–261 glycosyl fluorides 137 hydroxypyruvate (HPA) 315, 316 glycosylation 133 glycosylazides 137 i glycosyltransferases (GTs) 134–135, 139, (S)-ibuprofen 208, 213 147, 149, 150, 377, 378 iminocyclitol synthesis 340–351 glycosynthases 136–137 immobilization, enzyme 220–222 guanosine monophosphate (GMP) 148 immobilization techniques evolution 199–200 h in situ enzymatic recycling, NAD(P)(H) Heck reaction 448 cofactors 23–38 Henry reaction 350, 438, 439 in situ nitrile hydratase/amidase enzymatic heparin 144 system 283 heparosan 144 in situ product removal (ISPR) technique 30, (R)-heptanol and heptanone synthesis 118 31, 241 high-redox potential laccases (HRPLs) 3, 5, 6 in situ regeneration of oxidized NAD(P)+ – directed evolution of ligninolytic 8–11 cofactors 31–37 high-throughput screening (HTS) 2, 8, 10, in situ regeneration of reduced NAD(P)H 15, 316, 318, 321, 326, 376 cofactors 24–31 hollow fiber membrane bioreactor 208, 210 in vivo assembly of mutant libraries (IvAM) β -homoalanine 161 14, 16 Horner–Wadsworth–Emmons olefination in vivo metabolism 329 reaction 439 in vivo multistep biocatalysis 51–56 horse liver alcohol dehydrogenase (HLADH) in vivo overlap extension (IVOE) 14, 16 204 induced resistance defense mechanism 161 horseradish peroxidase (HRP) 12 inorganic phosphite oxidation 26 hyaluronan oligosaccharides 144 ion-exchange-polymer-catalyzed epimerization hydantoinase process 162–164 59 hydantoins, 5-monosubstituted 162, 163 L-isoaspartate 398 hydrogenase 27–29 -catalyzed acylation 211, 213 hydrolase-catalyzed continuous-flow k techniques 214 ketones 67, 260 hydrolase-filled continuous-flow reactors – oxidation 50 215–217 – reduction 202, 448 203, 207, 211 (S)-ketoprofen 208 hydrolytic enzymes 203, 410 kinetic resolutions (KRs) 66–67, 179, 208, hydrolytic processes, in continuous-flow 210–220, 222, 299 system 211 hydrolytic reactions 202, 208 l ω-hydroxy acids 50 laccase-catalyzed biotransformation 450, 452 β-hydroxy nitriles 251 laccase-mediator systems 7 2-hydroxy-γ-butyrolactone (HBL) 208 laccases hydroxyacetone (HA) 349–354, 356 – blood-tolerant 9 hydroxyaldehyde 321 – directed evolution of 6–11 hydroxybutanone (HB) 349, 352–354 – PM1 8, 10, 11, 16 (S)-2-hydroxycarboxylic amides 262 β-lactam carbonitriles 251 hydroxylation reaction, P450 monooxygenases β-lactam-recognizing enzymes (BLREs) 307 88, 89 lactate dehydrogenase (LDH) 28, 31–32 5-hydroxymethylcytosine (hmC) 404 layered double hydroxides (LDHs) 322 hydroxynitrile lyase-nitrilase 259–261 LecitaseⓇ Ultra 208 462 Index

Leloir pathway 363, 366, 367, 372, 389 – cofactors 400–403 Leloir-glycosyltransferases 134, 135 – higher homologs and derivatives 403–406 Leloir-path sialyltransfer enzymes 368 – radical-SAMenzymes 395–396 – substrates 396–400 – combustion 3 N-methyltransferases (NMTs) 414, 417 – degradation 3, 5 Michaelis–Menten kinetics, PFR type reactor lignin peroxidases (LiPs) 3, 5, 11 200–201 lignin polymer 5 microbial transketolase 315 ligninolytic enzymatic consortium 1, 3–6 microreactor technology 199, 203 ligninolytic high-redox potential laccases, mining genomes for nitrilases 271–279 directed evolution of 8–11 mitochondrial CYP11B2 93 ligninolytic 1–17 mitochondrial cytochrome CYP11A1 92, 93, ligninolytic peroxidases 11 95 lignocellulosic materials 6 Mn peroxidases 11 Li-HPA 325, 326, 330 molecular oxygen fixation, monooxygenases linear cascade reactions 69–82 44 lipase-catalyzed acylation 212, 213 monooxygenase-catalyzed redox cascade lipase-catalyzed hydrolytic reactions 252 biotransformations 43–61 lipase-catalyzed kinetic resolution 212 monooxygenated metabolites 97 lipase-catalyzed reactions 204 5-monosubstituted hydantoins 162, 163 lipase-nitrile hydratase-amidase 263–264 5-and 6-monosubstituted dihydrouracils lipases 207, 211, 231, 299–300, 450 (DHUs) 162, 164, 165 low-redox potential laccases, directed multienzyme system evolution of 7 – biocatalyst options 233–237 – classification 233, 234 m – compartmentalization 237 mediator-coupled enzyme systems 35–37 – process control 244 medium-redox potential laccases, directed – process development 239–244 evolution of 7–8 – process engineering 241 membrane bioreactors (MBRs) 201, 208, 210 – process modeling 241–244 metabolic diversification 385 – transport limitations 235–237 metabolic engineering 16, 385, 409 multistep cascade reactions 87–88 metal catalysis 445–449 multistep oxidations catalyzation metal catalysts 283, 430, 432, 433, 436, 445 – multiple P450 102–108 metal-catalyzed hydrogenation 446 – single P450 92–101 metal-catalyzed racemization 431, 433 mutagenesis, site-directed 134, 135 metal-catalyzed transformation 449 mutagenic organized recombination process metallo-enzymes 302 by homologous in vivo grouping metathesis 449 (MORPHING) 14–16 α-methionine 172 Myceliophthora thermophila laccase (MtL) 7, methyl dodecanoate 72 8, 16 methylation 393, 394, 398, 400 methylene groups oxidation 49, 50, 119 n methylenedioxo motif 416 NAD(H)-dependent dehydrogenases 3-methylthietan-2-one hydrolysis 207 317–319 O-methyltransferase (OMT) 410, 414, 416, NADH cofactor regeneration 28 417 NAD(P)H oxidases (NOXs) 32–34 methyltransferases (MTs) 393–417 NADH regeneration 30, 37 – bacterial 404 NADH-dependent dehydrogenase 318 methyltransferases, S-adenosyl-L-methionine NAD(P)H-dependent dehydrogenases 23 (SAM) dependent (S)-naproxen 208, 210 – acting on small molecules 398–400 natural cascades 250–257 – cascade applications 410–415 neo-sialoconjugates synthesis 378–388 – cofactor (re)generation 406–410 neuraminic acid 370 Index 463 neuraminic acid aldolase (NeuA) 368–371, oxoesters, dynamic kinetic resolution of 381, 383, 385 185–188 neuraminic acid synthase 371–372 oxy-functionalized heteroaromatic compounds nicotinic acid 254 452 nitrilase-amidase 258–259 oxygenase-nitrilase 262–263 nitrilase-catalyzed transformations 272 oxynitrilase. See hydroxynitrile lyases (HnLs) – hypothetical mechanism of 273 nitrilases 258, 271–272 p – analysis of specific regions 276 packed bed reactor (PBR) 208, 218–220, 222, – bacterial 274 237, 238 – enzyme mutants analysis 276–277 – in hydrolase-catalyzed acylation 213 – in fungi 274–275 – hydrolysis in 208 – mining genomes for 271–279 Pasteurella multocida hyaluronan synthase – in plants 275 (PmHAS) 144–145 – properties and applications 277–279 pathway engineering 121, 122, 414 – sequence clustering 275–276 – sequences diversity 272–274 peptide glycosylation 151 – structure and mechanism 301 peptidomimetics 297–298 – structure-function relationships in peroxidases and peroxygenases, directed 275–277 evolution of 11–15 – substrate selectivity 302 peroxygenases, unspecific 3, 15, 16 nitrile containing compounds 249, 250, 264 phenol red 326–329 nitrile converting biocatalysts 300–301 phenylacetonitrile 257 nitrile converting enzymes 249–265 phenylglycine methyl ester, ammonolysis of nitrile hydratase-amidase 250–255, 257–258 186 nitrile hydratases (NHases) 250, 251, 302 phenylpropanoids 410 – activity and stability 287–289 phosphatase-catalyzed reaction 439 – cascade substrate selectivity 304–308 phosphite dehydrogenase – structure and mechanism 303 (PTDH) 26–27 ′ ′ nitrile hydratases-amidase bi-enzymatic 5 -phosphoadenosine 3 -phosphosulfate cascade system 284–287 (PAPS) 146 nitrile hydrolysis enzymes 301 phosphoenolpyruvate (PEP) 364 Ni-nitrilotriacetic acid (Ni-NTA) complex 207 phosphoglucomutase (PGM) 139 non-nucleoside reverse transcriptase inhibitor physiological cascade reactions, P450 96 91–108 nonstereoselective enzymatic processes 204 α-pinene 114, 115 nucleoside diphosphate (NDP) 146 L-pipecolic acid 442 nucleotide activation of sialic acids 372–373 plug-flow reactor (PFR) 200, 201 nucleotide sugars 135, 139–141, 146–148 PM1 laccase (PM1L) 8, 10, 11, 16 polyacrylonitriles (PANs) 255 o polyhydroxylated compounds 351–355 omeprazole metabolism 102–103 poly-LacNAc oligomers 151 one-pot reduction–oxidation–hydrolysis poly-LacNAc structures 54 – convergent synthesis of 152 one-pot synthesis 134, 138, 146–151, 258, – one-pot synthesis of 143 379–385 polymerase chain reaction (PCR) 2, 26 – of poly-LacNAc structures 143 polyphenol oxidase 321–322 opium alkaloids 415 polyphenoloxidase (PPO) biosensor 322–324 organocatalysis 231, 440, 449–452 poly(ethylene glycol) (PEG)-polymer 149 organocatalytic dehydration 440 poly(ε-caprolactone)-type polyester 446 organonitriles detoxification 283 porcine pancreas lipase (PPL) 213 orthogonal cascades 44 post-synthetic diversification 386–387 oxazinone hydrolysis 438 potential reactor configurations 238 -catalyzed reactions 442 process engineering 241 464 Index

prochiral diols, enantioselective acylation of s 212 Saccharomyces cerevisiae biomolecular tool box profen thioesters deracemization 189 15–16 progesterone oxidation 116 selenium-based cofactor analog 404 promiscuity 169 self-supported chiral titanium cluster (SCTC) protein engineering 2, 24, 37, 65, 87, 124, catalyst 203 135, 137, 144, 180, 240, 241, 244, 245, 346, sialoconjugate arrays applications 388 356, 384, 389 sialoconjugate diversity 361–389 protein methylation 400 sialoconjugate libraries 363–378 protein molecular models 350 sialoconjugates, 5-or 9-fluorophore-labeled protein processing, maturation and exocytosis 381 13 sialyl acceptor 378–379 proteins arginine-N-methyltransferase sialylated oligosaccharide 361, 362, 383 (PRMT) 398 sialylation 361, 383 proteomics 203–204 sialyltransfer reactions 382 Pseudomonas cepacia lipase (PcL) 207 sialytransferase (SiaT) 364, 377–379, 381, Pseudomonas fluorescens lipase (PfL) 212 383 putative racemization mechanism 190 Sinorhizobium meliloti (SmelDhp) 163–165 putrescine-NMT 414–415 sitagliptin 298 Pycnoporus cinnabarinus laccase (PcL) 8, 10, staggered extension process (StEP) 14, 16 11, 16 stereoselective acylations 211–220 pyrene oxidations 97, 99 stereoselective carboligation 330 pyridinedicarbonitriles 253 stereoselective enzyme reactions 204–222 pyridoxal phosphate (PLP) 66, 185, 186 stereoselective hydrolase-catalyzed process – catalyzed racemization 436 199–222 pyridoxamine-5′-phosphate (PMP) 66 stereoselective hydrolytic reactions pyrolytic graphite (PG) particles 28 207–211 stereoselective synthesis –ofβ-amino acids 297–309 r –of14(S),15(R)-epoxyeicosatrienoic acid racemization, amine-catalyzed 438 110 reaction engineering 181, 194, 453 – of epoxyhexane 111 reactor configurations, potential 238 steroid 11β-hydroxylase. See mitochondrial recombinant DNA (rDNA) technology 240 CYP11B2 redox and redox-neutral cascade reactions Strecker reaction 203, 254 70–75 styrene monooxygenase (SMO) 46, 47 redox chromophore 325–326 β-substituted β-adrenergic agents 297 redox systems, P450 monooxygenases 89–90 substrate binding model 373–376 redox toolbox concept 56 substrate engineering 181, 183, 194 redox-balanced biocatalytic system 45 substrate-binding interactions 375 regio-and stereoselective dihydroxymyristic substrate-coupled approach 29 acid synthesis 109 subtilisin-catalyzed process 214 L-rhamnulose-1-phosphate aldolase (RhuA) synthase (SuSy) 146 341, 342, 344–349 Suzuki reaction 446–448 rhodium catalyzed racemization 431 Rhodococcus erythropolis A4 252–254, 258, 264 t Rhodococcus erythropolis AJ270 251, 253 tamoxifen metabolism 104, 106, 107 Rhodococcus rhodochrous PA-34 whole cells taurine 161 255 taxol 120, 122 (R)-rhododendrol 448 synthesis 382 D- 5-phosphate (D-R5P) 317, 330 tetrazolium red 325 RNA methylation 400 thermophilic alcohol dehydrogenase (TADH) ruthenium catalyzed racemization 432, 433 206 Index 465 thiamine diphosphate (ThDP)-dependent umbelliferone 320 enzyme 315 unspecific peroxygenases (UPOs) 3, 15, 16 thioesterification 184 β-ureidopropionase. See N-carbamoyl-β-alanine thioesters 180 amidohydrolase (NCβAA) – dynamic kinetic resolution of 188–193 D- 352, 355 v toluene oxidation 52 vanillin 53, 414 Trametes versicolor laccase (TvL) 11 verapamil metabolism 102 transaminases 300 veratryl alcohol (VA) 3, 11 ω-transaminases (TAs) 65–83, 207 versatile peroxidases (VPs) 5, 11–13 – cascade reactions 80–82 vitamin D3 metabolism 107 – catalyzed amination 77 – catalyzed reactions 68, 69 w – linear cascade reactions involving 69–72 Wacker oxidation 448, 449 α-transaminases 66 whole-cell biocatalysts 114–115, 235, 250, transamination 203 252, 253, 260 transglycosylation 136, 142, 151 wild-type FucA 343 transition-metal-catalyzed heterogeneous wild-type transketolase 330–331 hydrogenation 59 Wittig reaction 443, 444 transketolase (TK) 207 – activity by in vivo selection 329–330 x – activity in E. coli 331–334 xenotransplantation antigen glycan synthesis – activity in vitro 317–329 148–149 – applications of 315–335 xylene-monooxygenase (XMO) 52 – microbial 315 xylulokinase (XK) 318 phosphate (TPI) 317 D- 5-phosphate (D-X5P) 317, 318 u UDP-Gal and UDP-GalNAc synthesis 142 ultra low molecular weight (ULMW) heparin 145