445

Index a α-alkyl acrylates 175, 176 AADH 252 α-aminobutyric acid 366 AADH vs. AmDH 254 α-aminophosphonates 357 2-acetamide-2-deoxyisosorbide (ADI) α-aminophosphonic acids 357 343 α,β-unsaturated 2-acylimidazoles 3-acetamido-5-acetylfuran (3A5AF) 177 343 AmDH (amine dehydrogenase) 128, 2-acetamido-2-deoxysorbitol (ADS) 129, 252–262 342 amine dehydrogenase (AmDH) 128, acrylamine 344 129, 252–262 active pharmaceutical ingredients cascade reactions (APIs) 12, 25, 158, 161, 188, biocatalytic hydrogen borrowing 246, 399, 431–435 261 alanine 127, 257, 262, 361, 364–366 chemoenzymatic cascades 262 alanine dehydrogenase (AlaDH) 127 multi-enzyme cascades 261–262 alcohol dehydrogenases (ADH) 128, leucine dehydrogenase 253–254 129, 261 native amine dehydrogenase alfuzosin 367 254–256 aliphatic amines 67, 74, 131, 133, 244, phenylalanine dehydrogenase 254 289, 312, 355, 357 substrate promiscuity aliphatic N-nitrosamines 432 amino alcohol synthesis 260 alkanolamines 348–350 reductive aminase activity alkene-alkyne (enyne) metathesis 139 259–260 alkyl amines 306, 307 synthetic applications capping agents 322–325 primary amine synthesis 256–258 displacement, of amines 325 amidyl radical addition 55–62 alkyl aryl ketones 160 amination via N-atom nucleophilic alkylazo compounds 432 addition α,α-disubstituted benzylamine aromatic C(sp2)-H bonds amination picolinamides 396 77–82

Methodologies in Amine Synthesis: Challenges and Applications, First Edition. Edited by Alfredo Ricci and Luca Bernardi. © 2021 WILEY-VCH GmbH. Published 2021 by WILEY-VCH GmbH. 446 Index

amination via N-atom nucleophilic 3-amino-1,2,4-triazole 358 addition (contd.) 2-and 4-nitrocumene 428 benzylic C(sp3)-H bonds amination aniline 382 85–87 synthesis 403 N-α-C(sp3)-H bonds amination annulated aniline derivative 382 87–90 anti-cancer alkaloid proximicin A olefinic C(sp2)-H bonds amination 344 82–85 anti-cancer drugs 367 amination via radicals cross-coupling antihypertensives 352 aryl C(sp2)-N bonds formation via antiseptic agents 352 radicals cross-coupling 94–96 arene amination 392, 393, 397, 398, C–N bonds formation 96–98 400 arene nucleophiles 390 using diarylamines 91 arginine and ethylenediamine (NCDs) amine-functionalized graphene (AFG) 312 299 CD-supported amines 315 amine oxidases (AOs) 103, 155, 214, one-pot functionalization 312, 313 243–252, 266, 274 post-functionalization 313–315 amines aromatic amination reactions and formamides synthesis 345–348 human pharma application aminium radical cation addition 432–433 64–71 recycling of metals, ligands and other amino α-carbanion 204 cost drivers of 434 aminoalkylphenol derivatives 367, regulated part of new drug 368 applications 434–435 amino-functionalization, of CNO transition metal accounting 433 308–309 aromatic amines 68, 249, 354, 361, amino functionalized carbon-based 362, 377, 378, 415, 429, 431 nanomaterials 308–309 aromatic C(sp2)-H bonds amination 3-aminofuran 344 77 aminoketones 362, 364, 365 aromatic C–N bond formation 2-aminophenyl oxazoline 389 approaches 389 2-aminophenyl pyrazole 389 aromatic N,N-dimethyl tertiary amines amino pyrazole 387, 427 367 2-aminopyridine-1-oxide 389, 395 aromatization reactions 310 2-aminopyrimidine hydrochloride Arthrobacter nicotinovorans 252 426 artificial imine reductase (ATHase) 2-aminoquinazolin-4(3H)-one 418 247 8-aminoquinoline 389, 393, 395, 396 artificial transfer hydrogenases benzamide 393, 395 (ATHase) 267 8-aminoquinolinyl 404 arylamine formation 2-aminosugar 344 Chan-Lam coupling 428–429 Index 447

flow amination methods 431 asymmetric hydroaminoalkylation immobilization of 168–170 catalysts/supported catalysts asymmetric hydroaminomethylation 429–431 171–176 nucleophilic aromatic substitution asymmetric hydrogenation (AH) 156, 426–428 171, 172, 434 Pd-catalyzed C–N bond forming asymmetric reductive amination reaction 425–426 156–161, 267, 268, 274, 419 telescoped sequence of nitration and atomic force microscopy (AFM) 312 hydrogenation 428 attenuated total reflectance infrared arylamines 423, 426 (ATR-IR) 297 catalytic C–H amination 389–399 Au(I)/chiral Brønsted acid dual decarboxylative arylamination catalysis 421 405–407 aza-Michael reaction 194, 196 electrochemical approach 402–405 azomethine ylides 291, 292, 295, 305, hydroamination 419–424 307, 346 metal catalyzed cross couplings intermediate 291, 346 414–417 nickel catalyzed C–N coupling b 407–414 Bacillus badius 254, 256, 257 photoredox catalysis 399–402 Bacillus sphaericus 256 reductive amination 417–419 Bacillus steareothermophilus 253 syntheses 389 benchtop stable aminating reagent arylboronates 6, 7, 416 398 aryl bromide 167, 381, 384, 385, 409 benchtop stable ammonium carbamate aryl C–H amination 74, 390, 392–396, 400 398, 417 benzazepines 367–369 aryl C(sp2)-N bonds formation via benzomorpholine 350 radicals cross-coupling benzothiazine 350 other C–N bonds formation 96–98 O-benzoyl hydroxylamines 390 using diarylamines 91 benzylamine 87, 157, 246, 249, 252, aryl-diazonium salts 291, 304, 305 254, 295, 357 aryl fluorosulfonates 413, 414 benzylic amines 259, 318 aryl/heteraoaryl chlorides 412 benzylic C(sp3)-H bonds amination O-aryl hydroxylamines 401 85–87 aspartic acid 310, 311, 366 β-amidoester 344 Aspergillus Niger 214, 244, 245, 247, β-amino alcohols 350 255, 257 β-D-glucopyranosylamine 352 Aspergillus oryzae (AspRedAm) 128, β-1,4-glycosidic bonds 341 129, 268, 419 β-N-glycosidic bond 196 asymmetric hydroamination 162 B(C6F5)3-H2O catalyzed reductive alkene 162 amination 418 448 Index

biaryl based ligand BrettPhos 387 c biaryl monophosphine ligands 386 cadmium-catalyzed amination of bicyclic α-amino acid 214 iodobenzene 415 Biginelli reaction 357, 358 camptothecin (CPT) 307 Bingel–Hirsch reaction 299 Candida antarctica lipase B (CAL-B) bio-based 3,4-dialkoxyanilines 367 126 biocatalytic cascade synthesis 266 carbon-based nanomaterials 287 biocatalytic hydrogen borrowing 261, carbon, allotropes of 290 270 carbon nanostructures biodiesel production 361, 364 Au-NR 297 biorenewable aromatic monomers azomethine ylides, cycloaddition 366 291 bis(hydroxylmethylfurfuryl)amines chiral fullerene derivatives 291 (BHMFA) 355 glycidyltrimethylammonium 3,5-bis(trifluoromethyl)benzyl catalyst chloride 293 225 nanotechnological applications 2,5-bis(aminomethyl)furan (BAMF) 291 356 POM cluster 293 2,5-bis(hydroxymethyl)furan (BHMF) radical arylation reaction 291 356 functionalization procedures N,N′-bis(2-hydroxyethyl)-N,N′- 297–299 dimethyl-ethylenediamine carbon-based nanostructures 290, (BHEDMEDA) 349, 350 295, 297 1,3-bis(diphenylphosphanyl)propane carbon dots (CDs) 309 416 amines, as constituent 310–312 3,5-bistrifluoromethyl-benzaldehyde carbon nanocones 301 288 carbon nanodiamonds (CNDs) boron-doped diamond anodes (BDD) 305–307 404 carbon nanoHorns (CNHs) 301–305 2-bromonapthalene 411 carbon nanomaterials

bromotrichloromethane (BrCCl3)87 CND 305–307 Brønsted acid (BH) 90, 134, 135, 160, CNH 301–305 161, 165, 418, 421 CNO 307–308 Buchwald–Hartwig amination 378 carbon nano-onions (CNOs) 287, applications 386–388 307–308 catalyst design 385–386 carbon nanotubes (CNTs) 287, 290, limitations 384 291 mechanistic studies 384–385 1,1′-carbonyldiimidazole 190 Buchwald–Hartwig reactions 16, 430 carboxylic ND (ND-ori)-based Buchwald’s flow synthesis 426 supraparticles (ND-SPs) 307 bulky N-heterocyclic carbene (NHC) catalytic C–H amination 389–405 precatalyst 426 CD-promoted organocatalysis 315 Index 449 cellulosic biomass derivatives aryl C(sp2)-N bonds formation via 348–366 radicals cross-coupling 90–96 Chan–Lam coupling 378, 380–383, radical addition to C-C double/triple 428–429 bonds chemical vapor deposition (CVD) 301 amidyl radical addition 55–62 chemoenzymatic cascades 249, 262 aminium radical cation addition chimeric amine dehydrogenase 254 64–71 chiral amine frameworks 155 radical species addition to aromatic chiral amine (R)-α-methylbenzylamine rings 71–76 357 via N-radical species addition chiral amine synthesis, biocatalytic 54–76 strategies 244 cobalt-catalyzed C–H amination 395 chiral amino alcohol 387, 388 colorimetric test 289 chiral bisphosphine-thiourea ligand confocal fluorescence microscopy 158 297 chiral Brønsted acid 134, 160, 421, continuous Pd-catalyzed C–N coupling 422 process 426 chiral metal center 176–177 copper-catalysed heterocyclisation chiral N-arylamine 422 191 chiral pyrrolidinofullerenes 291 copper-catalyzed anti-Markovnikov chiral switch 155 hydroamination 423 chitin 341–345 copper-catalyzed asymmetric chitin-derived N-compound 343 hydroamination 422 chloropyrazine 427 C–H methyl bond 168 copper-catalyzed C–N coupling choline chloride-urea DES 345 reaction C–H pyridination-aminolysis sequence anticipated mechanism of 379 401 different conditions 380 ciprofloxacin 427 copper-catalyzed hydroamination cis-N-(2-methylcyclohexyl) 161 421, 423 ClMe2Si-IPr-Pd complex 430 copper-catalyzed primary aniline Clostridium sticklandii 258 synthesis 397 C–N bond formation copper-doped porous metal oxides amination via N-atom nucleophilic (Cu20-PMO) 367 addition copper(I) hydride catalysis 421 activated C(sp3)-H bonds copper-mediated decarboxylative amination 85–90 amination 406 aromatic C(sp2)-H bonds copper triflate 108, 291 amination 77–82 covalent functionalization 294, 295, olefinic C(sp2)-H bonds amination 303, 307, 314 82–85 cross-dehydrogenative coupling (CDC) amination via radicals cross-coupling 53 450 Index

Cu-catalyzed amination reagents 3 deep eutectic solvents (DES) 345, aminoboration of styrenes 9 369, 370 aryl boronates 7 dehydrogenative C–N couplings 91, aryl silanes 8 402 hydroamination of styrenes 10 density functional theory (DFT) 60, organolithium reagents 5 170, 316, 397 organozinc reagents 3 deoxyfructosazine (DOF) 345 silyl enol ethers 9 deoxyribonucleic acid (DNA) 297 via aryne intermedate 4 D-fructose 350 Cu-catalyzed annulative electrophilic D-galactose 350 amination 12 D-glucose 350 Cu-catalyzed C–H Amination of 3,4-dialkoxyanilines 367, 368 heterocycles 15 dialkylphosphinobiphenyl ligand Cu-catalyzed C–N bond-forming systems 430 approach 381 diarylamines 64, 91–94, 390, 391, 393 Cu-catalyzed electrophilic amination dibenzothiophene sulfoximine 396, of alkynes 11 397 Cu-catalyzed electrophilic dibenzylamine 108, 109, 215, 362 amino-lactonization 14 dibutylamine 355, 362 Cu-catalyzed electrophilic diamination dichlorobis(2,9-dimethyl-1,10-phenan- 13 throline)ruthenium (II) Cu-catalyzed ring-opening amination (Ru(DMP) Cl ) 354 14 2 2 (1,2-DCE) 74 cumidine 428 9,10-dicyanoanthracene (DCA) 85 Curtin–Hammett control 199 2,3-dicyano-5,6-dichlorobenzoquinone cyclic voltammetry (CV) 58, 61 (DDQ) 81 1,4-cyclohexadiene (1,4-CHD) 59 diethanolamine (DEOA) 350 cyclohexylamine 249, 357 cyclohexylamine oxidase (CHAO) diethofencarb 367 249 diethoxy(methyl)silane (DEMS) 167 cyclometalated iridium(III) complexes 2,5-diformylfuran (DFF) 357 393 2,5-diformylfuran dioxime 357 cyclopropylaniline 357 dihydroconiferyl alcohol 367, 369 dihydrofolate (DHF) 262 d dihydrofolate reductase (DHFR) 262 dahlia-like clusters 302 dihydrolipoic acid 328 dahlias 302 dihydropyrimidinones 357, 358 D-amino acid oxidase (pkDAO) 252 3,4-dihydropyrimidin-2-ones 358, 361 decarboxylation 131, 210, 211, 220, dihydrosinapyl alcohol 369 291, 345–348 1,3-dihydroxyacetone (DHA) 351 decarboxylative arylamination 2-(dimethylamino)ethanol (DMAE) 405–407 349 Index 451

4-(N,N-dimethylamino)pyridine Cu-catalyzed reactions 2–15 (DMAP) 198 hydroxylamine-derived 4-(dimethylamino)pyridine (DMAP) metallanitrenes 18–22 323 structure of 2 N,N′-dimethylethylenediamine transition metal free 22–27 (DMEDA) 350, 416 transition metals 15–18 di-(N,N-succinimidyl) carbonate 318 types of 2 dioctylamine 362 electrophilic diazonium salt 295 diphenylmethanamine 160 enamines 8, 118–120, 344 1,3-dipolar cycloaddition pathway enantioenriched α-and β-chiral 291 arylamines 422 dipolarophile 291 enantiomerically enriched chiral dipropylamine 362 secondary amines 421 diuretics 352 enantioselective A3 coupling 104–108 D,L-leucine 361 primary amines 106–108 D,L-phenylalanine 361 secondary amines 108–112 D,L-tryptophane 361 enantioselective C–H activation D-mannose 350 123–125 Doebner–Knovenagel reaction 189 enantioselective hydroamination 162, doxazosin 367 164 D-ribose 350 enantioselective hydrogenation, D5 variant 246, 247 photoredox synthesis 130–133 D-xylose 350 enantioselective rhodium-catalyzed dynamic kinetic asymmetric hydroamination 420 trasformation (DYKAT) 199 ene-reductase (ERED) 266 Engineered cytochrome P450s e 270–273 electrochemical approach 75, engineering functional nanomaterials 402–405 carbon-based nanomaterials, electrochemiluminescence (ECL) 314 functionalization of electron donor-acceptor (EDA) 34 carbon, allotropes of 290 electron paramagnetic resonance carbon nanostructures 290–297 (EPR) 89 functionalization procedures electron spin resonance (ESR) 319 297–299 electrooxidation cationic intermediates nanomaterial-bound amino groups 404 288–290 electrophilic amination environmental health and safety (EHS) arylcuprates, NH-oxaziridine 6 policies 425 via C–H cupration 7 enzymatic reductive amination 419 electrophilic amination reactions, enzymatic synthesis, propargylamines substitution-type 1 126–130 electrophilic amination reagents 1 epoxide hydrolase (EH) 262 452 Index

erlotinib 367 glucose dehydrogenase (GDH) 130, erythritol 342, 350 256, 264 ethanolamines 348 glutaric anhydride 201–203 ethylene diamine 125, 310, 348, 349 glyceraldehyde 351 4-ethylguaiacol 367 glycerol 361, 362, 364, 365 1-ethyl-3-methylimidazolium acetate glycolaldehyde 349, 350 345 gold(I) catalyzed hydroamination 421 ethynylbenziodoxolone (EBX) 130, gold-catalyzed intermolecular 132 hydroamination 420 evolution of, MAO-N 244–247 gold nanorods (Au-NRs) 297 Exiguobacterium sibiricum 256 gram scale nickel-catalyzed amination of 2-naphthyl bromide 411 f graphene 290, 295, 297–299, 308 fatty alcohols 370–373 graphene oxide 299, 430 fatty amines 319, 322, 371 graphite exfoliation, with melamine few layers graphene (FLG) 301 299–301 fiber-supported palladium dichloride/triphenylphosphine h catalyst 429 Hajos–Parrish–Eder–Sauer–Wiechert FibreCat 1026 429 reactions 188 fluorescein isothiocyanate (FITC) 303 N-haloamine 32 fluorescence correlation spectroscopy halopyridines 415 310 Hantzsch ester (HEH) 172, 421 fluoroalkylamines 386 1,5-H-atom transfer (1,5-HAT) 31 4-fluoroaniline 361 enthalpic effects 34 19F-NMR detection 288 geometrical factors 32 N-formamides 362, 364, 365 intramolecular 31–34 formamides 345–348 oxidative strategies formate dehydrogenase (FDH) 256 via amidyl and sulfamidyl radicals N-formyl amine 362 40–43 fossil-based feedstocks 341 via iminyl radicals 39–40 Friedel-Crafts-type arylation 135, photoinduced bond homolysis 138 43–46 fructosazine (FZ) 345 polar effects 34 fullerene derivatives 30, 291, 307 reductive strategies furan derivatives 352 via amidyl and sulfamidyl radicals furfurylamines 352–354 37–39 furosemide 352 via iminyl radicals 34 thermal strategies 46–49 g 5H-1-benzazepin-5-one 350 gefitinib 367 heat shock protein 90 (Hsp90) Geobacillus stearothermophilus 258 inhibitors 381 Index 453 hemicellulose-derived furfural 352 i (hetero-)aryl (pseudo-)halides 386 imatinib 425, 426 heteroatom doping 311 imine formation 160, 247, 268, 290, heterogeneous zirconium-based 318 catalysts 367 imine reductases (IREDs) 129, 244, hexafluoroisopropanol (HFIP) 21, 255, 262–270 84 imine reductases catalysing reductive horseradish-peroxidase (HRP) 308 amination 267 H2SO4/HNO3 nitration 431 immobilization of catalysts/supported human immunodeficiency viruses catalysts 429–431 (HIV) 297 indoline 59, 66, 115, 265, 423 hybrid organic-inorganic infrared spectroscopy (IR) 288 nanomaterials, amines 316 initial breakthrough in imine reductase alkylamines, semiconductor QD (IRED) 263, 268 319 biocatalytic cascade synthesis 266 capping ligands 321–322 catalysed reductive amination selenium-amine system 319–321 reactions 269 sulfur-amine system 319, 320 chemoenzymatic synthesis SAMs 316–319 265–267 hydantoin 344 engineering 267 hydroamination 8, 10, 11, 17, 54–56, inorganic ruthenium catalyst 293 58, 62, 66–69, 83, 162–164, in single-electron transfer (SET) 419–424 processes 130 hydrogen-atom transfer (HAT) 31–50, 55 in situ generated cationic Rh(III) hydrogen bond acceptor 287 catalyst 390 hydro-or solvo-thermal synthesis 309 inter-and intramolecular palladium 1-hydroxy benzotriazole (HOBt) 303 catalyzed C–H bond 6-hydroxy-D-nicotine oxidase functionalization 390 (6-HDNO) 252 intermolecular hydroamination 68, 1-hydroxyhexane-2,5-dione (HHD) 163, 420, 421 359 International Council of hydroxylamine-O-sulfonic acid Harmonization (ICH) 433 (HOSA) 20 iridium-catalyzed hydroamination hydroxyl moiety 315 165 5-hydroxymethylfurfural 352, 355 iridium-nitrenoid catalyzed C–H 5-hydroxymethylfurfurylamines 352 amination 393, 394 2-hydroxymethyl-5-methylpyrazine iron-catalyzed amination of aryl (HMMP) 351 halides 415 2-hydroxymethyl-5-methyl-pyrrole iron-catalyzed C–H functionalization moiety 359 397, 399 hypervalent iodine(III) 398 isophorone 346–348 454 Index

4-isopropyl phenol 428 Merrifield peptide resin 430 isoquinoline bromide coupling 387, meta-chloroperbenzoic acid (mCPBA) 388 5 isosorbide 343 meta-hydroxyacetophenone 159 metal catalysed asymmetric synthesis j enantioselective A3 coupling Jørgensen–Hayashi catalyst 189 104–112 enantioselective C–H activation k 123–125 Kaiser test 288–290, 306, 312 Rh/Ru-catalyzed enantioselective ketimine reductases (KIREDs) 129, hydrogenation 120–122 267 terminal alkynes to kinetic isotope effect (KIE) 77 enamines/enamides 118–120 Knoevenagel condensation 315 metal catalyzed cross couplings 8, Knölker’s iron complex 421 403, 414–417 Kuznetsov method 307 metal or metal oxide nanoparticles 287 l 2-(methylamino)ethanol (MAE) 349 laser ablation 302, 305, 309 2-methyl cyclopentanone 161 leucine 253, 346, 366 methyl isobutyl ketone (MIBK) 253 leucine dehydrogenase (LeuDH) 2-methyl pyrazine (MP) 351, 352 253–254 microcontact printing 318 levulinic acid 360, 361, 364 microwave (MW)-induced method Lewis basicity 287, 322 295 lignin 366–370 monoamine oxidase 155, 214, 244, lignin-based aminoalkyl-and 249 aryl-guaiacols 369 monoamine oxidase A (MAO-A) 103 lignocellulosic biomass-derived monoamine oxidase from Aspergillus α-hydroxy acids 366 Niger (MAO-N) 214, 244 LiN(SiMe3)2 (lithium monoethanolamine (MEOA) 349 bis(trimethylsilyl)amide) 411 mono-substituted allenes 420 long-chain diols 372, 373 morpholine 354, 362, 429 luminescence 309 multi-enzyme cascades 261 luminophore 314 MW-induced double functionalization Lysinibacillus fusiformis 256, 260 296

m n macrocyclic secondary amines 327 N-acetonyl amines 362 maleic anhydride 291 N-acetylethanolamine 342 Meadows’ continuous synthesis 426 N-acetyl-L-rednose 344 3-mercaptopropyltrimethoxysilane N-α-C(sp3)-H bonds amination 87–90 (MPS) 326 N-acyl-propargylamines 145 Index 455

N-alkyl-substituted 2-hydroxymethyl- from chitin and its derivatives 5-methylpyrroles 359 341–345 N-alkyl tetrahydroisoquinolines lignin derivatives 366–370 (THIQs) 248 from triglycerides and fatty alcohols naphthalene bromide coupling 380 370–373 nanomaterial-bound amino groups nitrogen dioxide (NO2) 308 288–290 nitrogen (mostly amine)-doping 311 naphthalenoid H3 antagonist 380 nitrogen radicals 31–50 N-arylhydroxylamine esters 422 nitrosonium tetrafluoroborate

N-aryl-propargylamines 142, 143, (NOBF4) 291 145 15N-labeled compounds 288 N-arylpyridinium ions 403 N-mesylimidazole 404 native AmDHs (natAmDH) 254, 259 N-methylamines 362, 364 native amine dehydrogenase 254–256 N-methylamino acid dehydrogenases N-Boc-protected (NMAADHs) 129 amino-CNO-pyrrolidine 307 N-methyldiethanolamine (MDEA) N-ethyl-N′-(3-(dimethylamino)propyl) 350 carbodiimide hydrochloride N-methyl-O-tosylhydroxylamine 392 (EDC) 303 N-methylpyrrolidine derivative 291 neurodegenerative diseases 297 N-modified α-amino acids 303 N-heterocyclic carbenes (NHC) 385, N,N-dimethyl-1-(3,4,5-trimethoxy- 408 phenyl)methanamine 367 N-heterocyclic chemicals 345 N-octadecylaniline 371 N-heterocyclic compounds 351 non-cross-linked polystyrene (solPS) N-hexadecylaniline 371 supported SPhos (solPS-SPhos) Ni(NHC)-catalyzed amination of 429 aryl/heteroaryl chlorides 409 N-(p-tolyl)benzophenone hydrazone Ni-catalyzed aryl amination chemistry 386 408 N-substituted Ni-catalyzed C–N cross-couplings 5-hydroxymethyfurfurylamines 408, 409 353 nickel-catalyzed amination 408–414 N-substituted 2-hydroxymethyl-5- nickel catalyzed C–N coupling methylpyrroles 359 407–414 nuclear magnetic resonance (NMR) nickel-mediated C–H amination 395 techniques 172, 288, 315 Ni(allyl)(IPr)Cl 410 nucleophilic aromatic substitution nitrene 18, 125 312, 377, 426–428 nitrilotriacetic acid (NTA) 297 nitrogen compound synthesis o from α-amino acids 345–348 1-octadecene (ODE) 319 from cellulosic biomass derivatives O-(2,4-dinitrophenyl)hydroxylamine 348–366 (DPH) 20 456 Index

olefinic C(sp2)-H bonds amination 82 phenylalanine dehydrogenase organic-inorganic hybrid (PheDH) 253, 254 nanomaterials 287 phenylallene 421 organic-inorganic hybrid nanoparticles (S)-1-phenylethylamine 202 328 photocatalysis 131, 178, 400, 416, 418 amines 325–328 photocatalytic perfluoroalkylation post functionalization of amine 315 328–329 photodeprotection reactions 318 organocatalyic C–H oxidative photoinduced electron transfer 402 amination 398 photoinduced strategies organocatalysis 187–231 oxidative strategies organocatalytic stereoselective 1,5-HAT via amidyl and sulfamidyl synthesis 134 radicals 40–43 organolithium reagents 4, 5 1,5-HAT via iminyl radicals organozinc reagents 2, 3, 15 39–40 ortho-aminobenzoic acid derivatives photoinduced bond homolysis 396 43–46 oxazoles synthesis 145 reductive strategies oxazoles thiazoles 148 1,5-HAT via amidyl and sulfamidyl oxygen reduction reaction (ORR) 299 radicals 37–39 1,5-HAT via iminyl radicals p 34–37 Paal-Knorr reaction 359 thermal strategies 46–49 Paenibacillus lactis 265 photoredox catalysis 37, 54, 73, 77, palladium amine complex 385 78, 81, 130, 150, 399–402 palladium catalyzed aryl C–H photoredox catalysts 69, 176 amination 390 photoredox catalyzed C–N bond paloxetine 412 forming processes 401 Pd-catalyzed C–N bond forming photoredox synthesis, propargylamines reaction 425–429 130 Pd/Cu bimetallic catalytic system 406 Pictet-Spengler cyclization 369 Pd nanoparticles on silica-starch Pinnick oxidation 205 substrate (PNP-SSS) 430 p-methoxyphenyl (PMP) 56 penicillin G amidohydrolase (PGA) polar effects 34 127 poly(vinylpyrrolidone) (PVP) 324 peptide-like heterocyclic molecules polyallylamine 322, 326 361 polyamidoamine (PAMAM) dendrimer Petrotogamobilis 254 302 phase-transfer catalysed (PTC) 187 polyethylene glycol-anchored phenol-derived electrophilic arene phosphine ligand 429 coupling partners 412 polyethyleneimine (PEI) 322 phenylalanine 253, 254, 366 polymeric coating 326 Index 457 polymethylhydrosiloxane (PMHS) 8, quinolines synthesis 142–145 409 synthetic methods 104 polysaccharide xylan 353 propionate esters 367 polyvinylpyridine (PVP) supported 4-propylcatechol 367, 368 catalyst 430 4-propylguaiacol 367, 368 porphyrin 303, 314, 328 prostate specific membrane antigen Potential Genotoxic Impurities (PGIs) (PSMA)+ cancer cells 304 211 proton-coupled electron transfer prazosin 367 (PCET) 40, 55, 176 pregabalin proximicin A 344 acetate enolate equivalents to pseudo-peptides 361

nitroalkene 206–214 P(Ar)3-type ligands 384 amino α-carbanion to Michael pyrazines 345, 351, 352 acceptors 204–206 pyrazole 77, 80, 381, 387, 389, 427 glutaric anhydride 202–204 pyridazinium chloride 387 pristine C60 fullerene 291 pyridazinone 380 prochiral aminoketones 362 pyridines synthesis 140 proline-based catalyst and pyridinium chlorochromate (PCC) p-nitrobenzoic acid (PNBA) 174, 215 134 pyrimidine 166, 196, 404 propargylamines 103 pyrolysis 309 enzymatic synthesis 126–130 pyrroles 71, 72, 80, 81, 103, 137–139, metal catalysed asymmetric synthesis 358, 359 alkynyl-substituted moiety 291 epoxides/lactones/carbonates pyrrolidine 346, 360 116–118 pyrrolidinofullerenes 291 enantioselective A3 coupling pyrrolidones 12, 360, 361 104–112 pyrrolines synthesis 139 enantioselective C–H activation 123–125 r Rh/Ru-catalyzed enantioselective racemic isocyanides 361 hydrogenation 120–122 radical addition to C-C double/triple terminal alkynes to bonds enamines/enamides 118–120 amidyl radical addition 55–62 organocatalytic stereoselective aminium radical cation addition synthesis 134 64–71 oxazoles synthesis 145–147 radical arylation reaction 291 oxazoles thiazoles 148–150 radical species addition to aromatic propargylic amination reaction 112 rings 71–76 pyridines synthesis 140–142 Raman spectroscopy 319 pyrroles synthesis 138–139 reductive aminases (RedAms) 268 pyrrolines synthesis 139–140 reductive amination 417 458 Index

reductive amination (contd.) Sphingobium yanoikuyae (SyADH) aldehyde/ketone 156 128 aldehydes 173 sp2-hybridized carbon atoms 290, intramolecular asymmetric 295 158 (S)-selective amine oxidases 2-methyl-6-ethyl-aniline 157 CHAO 249–251 reductive amination reaction 128, MAO-N 244–247 156, 158, 417 Pseudomonas monteilii ZMU-T01 renewable polyamides 355 249 Rh-catalysed hydroaminomethylation synthetic applications and cascades 171 247–249 rhodium-catalyzed C–H amination sterically encumbered 390, 392 N-adamatylbenzamide 393 Rhodococcus sp. 253, 256, 257, 259 Stradiotto’s and Hartwig’s (R)-selective amine oxidases nickel-catalyzed amination D-amino acid oxidase 252 411 6-HDNO 252 Streptomyces virginiae 254 Ru-catalyzed C–H amination 17 styrene monooxygenase-catalysed Ruhemann’s purple 290 (SMO) 262 ruthenium-based photocatalyst 2,5-substituted pyrrolidines 167 401 sulfamates 412 ruthenium catalyzed C–H amination sulfonamide 45, 56, 71, 72, 80, 81, 91, 403 99, 166, 167, 344 sunflower oil 371 s supercritical fluids 299 Schiff base adduct 346 superficial amines 294, 297, 308, self-assembled monolayers on flat 314 surfaces (SAMs) 316–319 semiconductor quantum dots 287, t 316, 319–322 Tamibarotene 382, 383 Shvo’s catalyst 369 t-butyl[(1,1′-biphenyl)-2-carbonyl] silane reductant 409, 418 oxycarbamate 406

silica supported SiO2-SPhos 429 telcagepant 189, 190, 221, 231 silyl enol ethers 9, 26, 27 telescoped sequence of nitration and single electron transfer (SET) 35, 55, hydrogenation 428 130, 176, 395 terazosin 367 single-walled carbon nanotubes terminal alkynes to (SWNTs) 291, 293, 307 enamines/enamides 118–120 spectrophotometric detection 288 tert-butyl 2-(2-(2-aminoethoxy)ethoxy) spectroscopic techniques 288, 289 ethylcarbamate 303 Index 459

2-tert-butylanthraquinone transmission electron micrographs (2-t-Bu-AQN) 72 301, 302 tert-butyl (2-(2-(2-(4-aminobenzamido) transmission electron microscopy ethoxy)ethoxy)ethyl)carbamate (TEM) 297 305 2,4,6-triamino-1,3,5-triazine 301 tert-butyl hydroperoxide 197 triazacyclononane or chelating amines tert-butyl nitrite (TBN) 81 327 tetrahydroisoquinolines 130, 158, trichloroacetic acid 318 247, 248, 250 triethanolamine (TEOA) 350 N,N,N′,N′-tetramethylethylenediamine trifluoroacetic acid (TFA) 42, 80, 192, (TMEDA) 350 299 thermal cycloelimination 291 trifluoromethanesulfonamide (TfNH2) Thermoanaerobacter ethanolicus 83 (TeSADH) 128 5-(trifluoromethyl)-2-isoxazolines thermogravimetric analysis (TGA) 223–230 288 triflyloxy pyridinium 401 thiohydantoin 344 triglycerides 370–373 threshold of toxicological concern triisopropylsilane (TIPS) 324 (TTC) 432 2,4,6-triisopropyl-thiophenol (TRIP tin-free Pd-catalyzed coupling 384 thiol) 56 TM-catalyzed electrophilic amination trilaurin 371 2, 15 3,4,5-trimethoxybenzaldehyde 367 TM-free Prilezhaev reaction 26 trimethylsilylamino derivatives 291 TM-free Rubottom oxidation 26 tri-n-octylphosphine (TOP) 319 Tofacitinib 159 tri-n-octylphosphine oxide (TOPO) topaquinone (TPQ) 243 319 top-down methods 309 2,2,5-triphenylpent-4-en-1-amine transaminases (TAs) 243, 244 166 transition metal accounting 433 2,4,6-triphenylpyrylium (TPT) 93 transition metal catalyzed C–N 5,10,15-tris(3,5-di-tertbutylphenyl)- coupling 20-[4-(carbonyloxy)phenyl] aromatic amines 377 porphyrin 303 Buchwald-Hartwig amination tryptamine 346, 361 383–388 2-D self-assembled monolayers 287 nucleophilic aromatic substitution 377 u substituted aromatic amines 377 Ugi three-component condensation Ullmann-type amination 378–383 reaction 361 transition metal (TM) free amination Ullmann-type amination 22 applications 380–383 460 Index

Ullmann-type amination (contd.) w catalysts and variants 380 waste treatment 425 mechanistic studies 379–380 Wilkinson’s catalyst 291 urea 59, 163, 344 x v X-ray photoelectron spectroscopy valine 346, 347, 366 (XPS) 288 van der Waals-like forces 301 xylan 353, 358, 359 vinylarenes 423 xylitol 350 VLA-4 antagonist 403, 405