515

Index

aAc2O 209acetalization, DMF 294acetamidation 238acetic acid catalysis, amidation 238acetone

C-nucleophile 173Michael addition reactions 168, 178multicomponent reactions 177

acetonitrile 278free radical initiated C–H

functionalization 373transition metal catalyzed cross

coupling 355–366acetophenone-derived

benzoylhydrazone 278acetylation, DMF/DMAc 2853-acetyl-2-aminothiophenes 251acetyl moiety, amidation/thioamidation

using 227–2311-acetyl-N-phenylcyclopropane-

carboxamide 2523-acetyl-1-phenylpyrrole 285acid chlorides 286acidic ionic liquid ([NMP]H2PO4) 413AcOH 208, 218AcONa/p-MeC6H4NH2 202acridine red 98acyl chloride 211acyl halides, amidation of 210–211acyloxylation 2351-acyl-2,4,6-trihydroxybenzene 243aerobic copper catalysis

methylidynation 284Ag2CO3 207, 269

Ag2O 278AgSCF3 293AIBN 61, 106alcoholsα-C–H functionalization 422, 425β-amino 166C-nucleophiles 191amidation of 233–234application of 77catalytic transesterification reactions

186electrophile, see electrophileethyl acetate 183homogeneous catalysis 403L-proline 163location of hydrogen atom 403O-nucleophile, see O-nucleophileoxidation 421–422VR-mediated formylation of

246–247aldehydes 99, 166, 356

amidation of 216–217, 234–235amination of 206, 207aromatic/aliphatic 163Brøsted acid 161selectivity 10

aldimine 264, 265aldol reaction 161–167aliphatic acids 96aliphatic amides 228, 229

carbonylation of 262, 263aliphatic hydrocarbons

C–B bond formation 506–507C–C bond formation

Solvents as Reagents in Organic Synthesis: Reactions and Applications,First Edition. Edited by Xiao-Feng Wu.© 2018 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2018 by Wiley-VCH Verlag GmbH & Co. KGaA.

516 Index

aliphatic hydrocarbons (contd.)alkane-aldehyde coupling

498–499alkane-alkene coupling 493–497alkane-alkyne coupling 497alkane-arene coupling 491–493alkane-arylboronic acid coupling

501alkane-carbene coupling 500–501alkane-CO-amine coupling

499–500alkane-isocyanide coupling 499alkane-ketone coupling 497–498

C–N bond formation 502–504C–O bond formation 504C–S bond formation 504–506

alkane-aldehyde coupling 498–499alkane-alkene coupling 493–497alkane-alkyne coupling 497alkane-arene coupling 491–493alkane-arylboronic acid coupling 501alkane-carbene coupling 500–501alkane-CO-amine coupling 499–500alkane-isocyanide coupling 499alkane-ketone coupling 497–498alkene 426, 428

amidation of 223, 237insertion reaction 271–272lithiation/borylation process 2visible-light initiated direct

oxysulfonylation 16visible-light-induced

hydrodifluoromethylation 6VR-mediated formylation of 245VR-mediated haloformylation 250

alkenyl halides, amidation of 209–210,231

alkyl aldehyde 180alkylalkenes 223, 237alkylation reactions 104–106alkyl ketones, methylenation of 283alkyne 428, 430

alkynes hydration 21amidation of 223–224

anti-Markovnikovhydrotrifluoromethylthiolationof 292

carbocyclization of 20hydration reaction 20insertion reactions 272–274[(NHC)AuI]-catalyzed 20oxidation 14substitution reactions 288

alkyne-azide 4alkynols 302-alkynylbenzaldoximes 91alkynyl trifluoromethyl sulfones 272allenes

halohydroxylation reaction 32hydroxyphosphinylation reaction 8

allyl acetates, amination of 205–206allylic bromides 285allylic ethers 86α-acyloxylation reaction 97α-amino carbonyl compounds 498α-amino ester 5α-arylnitriles 364α,β-epoxyalcohols 31α, β-unsaturated

acids, amidation of 213alkynoates 411esters, hydrogenation of 289perester, amidation of 213Weinreb amides 460

α-bromoamides 278α-C–H functionalization 422–424α-C–H hydroxyalkylation 107–1083α-cholestanyl acetate 2863α-cholestanyl formate 286α-carbamoyl α-oximyl cyclopropanes

259α-ketoacids, amidation of 211–216α-formyl ketones 247α-hydroxyacetophenone 217α-hydroxybutamides 258α-ketoacids 214

amidation of 235α-ketoamides 211, 213, 214α-oligo sulfide 215α-oxoacetamides 217α-oxocarboxylic acid 213

Index 517

α-silylcyclohexylcarbonitrile 358α-trimethylsilylcyclohexanecarbonitrile

360α-trimethylsilylpropionitrile 360alumina 228amidation 240

DMF/DMAc 209, 242VR-mediated 247

amides 478amidation of 225, 236–237

amidination, DMF/DMAc 241amidoalkylation 233, 237–239amidoalkyl naphthols 253amination 424–436

DMF/DMAc 200amine, amidation of 224, 235–237amine-aldehyde condensation 180amino acid esters 2281-aminodecane 2282-aminoethanol 2025-aminoisoxazoles 259amino-linked nitrogen heterocyclic

carbine (NHC) 4762-amino-4-oxazoline 277aminocarbonylation 232, 2332-aminopyridine 269aminopyrimidine 236aminothiazole derivatives 343ammonia (NH3) 53, 264, 266ammonium acetate 180anastrozole 357anhydrides

amidation of 211–216DMF/DMAc 286

anilines 230synthesis 180

anisole 243anthraquinone-2,3-dicarboxylic acid

56anti-Markovnikov 10–12, 33–35anti-Markovnikov

hydrotrifluoromethylthiolation292

ArCO2H 207arene 238

amidation of 238cyanation of 266

VR-mediated formylation of 243arene-alkene coupling

458–468arene-alkyne coupling 468–471arene-arene coupling 449–458arene-arylboronic acid coupling

476–477arene-CO-alcohol/amine coupling

477–478arenediazonium salts, selective

defunctionalization of 290arene-haloarenes coupling 471–476aromatic acids 96aromatic alcohols 364aromatic amides 228

carbonylation of 262aromatic bromides 260aromatic carbons, methylenation of

280–282aromatic cyanides 267aromatic esters 260aromatic halides 267aromatic hydrocarbons

C–B bond formation 484–487C–C bond formation

arene-alkene coupling 458–468arene-alkyne coupling 468–471arene-arene coupling 449–458arene-arylboronic acid coupling

476–477arene-CO-alcohol/amine coupling

477–478arene-haloarenes coupling

471–476C–N bond formation 478–482C–O bond formation 482–484C–Si bond formation 487–491

aromatic nitriles 265arylacetic acids 214aryl acetonitriles 250, 363, 478aryl aldehyde 180aryl–aryl and aryl–alkyl benzoin

benzoates 339aryl amines 2282-(arylamino)aryliminophosphoranes

284arylboronic acids 484

518 Index

aryl bromides 291amination of 203cyanation of 265

arylcarboxyamides systhesis 126-aryl-1,4-dithiafulvenes 2451-aryethanols 217aryl fluorides, amination of 203aryl halides

amidation of 209–210, 219–220,231

amination of 200–209aryl halides/tosylates 1824-aryl-4H-chromenes 413aryl iodides 269, 362

amination of 203carbonylation of 209cyanation of 265

aryl ketonesα-methylenation of 282methylenation of 283

aryllithium 260arylmetal/arylboron 109–1123-(1-arylmethylene)oxindoles 470aryl methyl sulfides 327aryl nitriles 264aryl olefins, hydroformylation of 258arylpalladium 232, 2913-arylpropan-1-ols 233arylquinones 465, 470aryl-tethered activated alkenes,

amidation of 227–231aryl thioaldehydes 219aryl thiols 223arynes, insertion reactions 274–276asymmetric Henry reaction 377Au catalysis

hydrogen delivery 292Au(III)-catalyzed 21Aza-Diels–Alder 19azidoborane 5027-azaindole 92azine heterocyles 177azoles 87, 88, 91, 92, 207–208

bB(OH)3/H2O 230benzaldehyde 17, 51, 217

benzamide 13, 14, 54, 211, 220benzamidines, methylidynation of 284benzannulation-diketonization 22benzene, Fridel–Crafts alkylation 49benzeneselenol 226benzimidazole 88, 284benzo[b]phosphole oxide synthesis

72–73benzofurans, cyanation of 269benzo[h]quinolines 453benzoic acids 235benzonitrile 14benzophenone derivatives 4571,4-benzoquinone (BQ) 10, 34, 353,4-benzo-1,1,2,2-tetraethyl-

1,2-disilacyclobutene 488benzothiazoles 87, 88, 222, 237, 240,

241amidation of 226amidoalkylation of 239amination of 207

benzothioaldehyde 217benzoxazole 88, 207benzoyl chloride 210, 272benzoyl cyanide 218benzoyl fluoride 9benzoyl peroxide (BPO) 61benzyl acetates, amination of 205–206benzyl alcohols 17benzylamine 206, 219benzyl bromide 287benzyl chloride, etherification of 2853-benzyl coumarins 66–67benzyl cyanides 218benzyl esters 64–65benzyl formate 287benzylic alcohols 405benzylic bromides 285benzylic carbons, methylenation of

278–280benzylic esters 484

synthesis 77benzylic halides, amination of 200benzylpyridines, α-methylenation of

2792-benzylpyrimidine 279β-alkoxide 413

Index 519

β-alkoxyketones 413β-alkoxy methyl sulfides 329β-amino ketones 336β-aromatic α-amino acids 73β-bromoacraldehydes 250β-chloroacraldehydes 2423β-cholestanyl tosylate 286β-dicarbonyl compounds, amidation of

221β-diketones 221β, γ-unsaturated esters 409β-haloacraldehydes 249β-hydroxyl ketones 163β-ketoesters 95, 221β-keto methyl sulfones 322β-nitroamine products 385β-nitroalcohols 378β-nitrostyrenes 106, 383BF3⋅Et2O 231BHT 83, 104[1,1′-biaryl]-2-amines 263bifunctional cinchona alkaloid thiourea

385bifunctional lanthanum-lithium chiral

binaphthoxide complex 377biologically significant trifluoromethyl

dihydroquinazolinones 3851,3-bis(carboxymethyl)imidazole 212bis(dichloromethyl)stannylene 1262-(bis(ethylthio)methylene)-

N-phenylbut-3-enamide 255bis(4-methoxybenzylthio)acetylene

24bisphosphine 289(bis(trifluoroacetoxy)iodo) benzene

(PIFA) 4931,3-bis-(2,4,6-trimethylphenyl)

imidazolium chloride(IMes⋅HCl) 184

bond dissociation energy (BDE) 366α-C(sp3)–H bond 81C–H 82ethers 118physical properties 81

borate salts 267boronate esters 267boron derivatives 229

boronic acids 267boronic ester 2boron trifluoride etherate 230borrowing hydrogen catalysis 233BPh3 catalysis

hydrodeoxygenation 295Brønsted acid catalyst 435Brønsted acidic ionic liquids 405Brøsted acid 161bromoamines 287bromoazide 2873-bromobenzotrifluoride 2092-bromobenzyl alcohol 260(4-bromobutyl)benzene, etherification

of 2852-bromoethylamines 287bromohydrins 3193-bromooxindoles, formyloxylation of

2882-(2-bromophenyl)acetonitriles 2093-bromopropylamines 287bromotoluene 219bulky biaryl phosphine ligands 415

cCandida antarctica lipase B (CAL-B)

184, 188carbamates 221, 222carbamic acid 230carbenes

insertion reactions 276–277ligands 486

carbonfrom dimethylamine moiety 262from DM dimethyl 266, 269from DMF carbonyl 264

carbon-hydrogen bond activationreactions 449

carbon monoxide 219, 260, 261carbonylation 209

carbon from DM dimethylaminemoiety 262–264

carbonyl from DMF 260–262carbonylation reagent 320–321carbonyl, from DMF 260carbonyl compounds, VR-mediated

haloformylation 249

520 Index

carboxylic acids 96, 97, 324amidation of 211–216, 235

carboxylic esters 190C2 arylated indoles 452catalytic α-arylation of nitriles 358catalytic asymmetric intramolecular

cyclopropanation (CAIMCP)15

catalytic asymmetric Michael reaction390

catalytic Friedel–Crafts benzylations432

C–C bondCDC 83formation 83–91

cellulose sulfuric acid (CSA) 177cerium oxide 228(CF3SO2)2 244(CF3SO2)2O 242, 246C–H bond

BDEs 81benzylic, carbonylation of 61direct functionalization of 83functionalization 51molecular oxygen 82of toluene and xylene 50

CH2CONMe2 moiety 233–241CHCONMe2 moiety 233–241chiral amino alcohol-Zn complex

catalyzed enantioselective Henryreaction 382

chiral spiro-pyrrolidine silyl etherorganocatalyst 390

chiral tridentate ditopic salen ligand380

4-chromanones 282chloroform reactions

with hydrogen fluoride 142phase transfer catalytic conditions

149with post-transition metals 142–143with transition metals 143–146

3-chloro-4-formylisoquinoleines 2503-chloro-3-phenylacrylaldehyde 2505-chloro-3-(phenylsulfanyl)pyrazin-

2-(1H)-ones 208

cis-2,5-diaminobicyclo[2.2.2]octane380

Cinchona-based squaramide catalyzedenantioselective aza-Henryreaction 385

cinnamic acid 215decarboxylative benzylation of 68

Claisen–Schmidt reaction 167–170ClCO2CCl3 242Cl3COCO2CCl3 242C–N bond formation 502–504C-nucleophile 403–411α-C–H functionalization 422–424oxidation 421, 422

cobalt-catalyzed cross-couplingreactions 474

C–O bondformation 93–97HI/HBr 81

Co catalysis, amidoalkylation 233CO2-catalyzed C–O bond activation

364COCl2 242copper 212copper acetate catalysis, amidation

238copper bromide 270copper-catalyzed

arylation/C–C bond activation 401,2-aryl migration reaction 3686-exo-trig cyclization 23, 24oxidative cyclization 9, 83, 95oxidative C(sp3)–H/N–H coupling

5041,2-oyalkylation 371sulphonamides, alkylation of 62–63

copper (II) catalyzed, chemoselectiveO-aroylation 55

copper-catalyzed 1,3-dipolarcycloaddition reaction (CuAAC)9

copper chelate 223copper nitrate 269copper perchlorate catalysis, amidation

211copper promoted

1,2-akylarylation 369

Index 521

1,2-oyalkylation 370copper tertiary amine complex

catalyzed Henry reaction 378core-chiral bisidines 378Co(ttp) catalysis, hydrogen delivery

293coumarin 66, 88–90, 256, 465coupling-ketooxygenation reaction 22Cp*Ir complexes 486CrCl2 94cross-dehydrogenative

alkylation 85arylation 87

cross-dehydrogenative coupling (CDC)82–97, 222, 223

C(sp3)–H bonds 85crotylation 278C–S bond formation 97–98Cs2CO3 209C(sp3)–H oxidative functionalization

101C2-symmetric bisoxazolidine 382Cu(acac)2 211Cu(OAc)2/t-BuOOH 213Cu(OAc)2/t-BuOOH/DMF 212Cu(OCOCF3)2 catalysis, methylenation

279Cu(OTf)2 catalysis, amidation 212,

224Cu(OTf)2-catalyzed N-nitrosation

394Cu(OTf)2-catalyzed arylmethylation of

benzylic alcohols 430Cu(OAc)2 catalysis

amidation 215, 222methylenation 279

CuBr 215, 225CuBr2 224, 234, 266Cu catalysis

amidation 213, 217, 221–223, 225methylidynation 283

Cu(I)-catalyzed 19CuI/t-BuOOH/DMF procedure

280Cu(II)-BOX complex catalyzed

asymmetric Henry reaction387

CuII-catalysisamidation 211amidation of 213

CuII/K2S2O8/DMF procedurein methylenation 282use in methylenation 281

CuII/t-BuOOH system 223CuII/t-BuOOH method 223Cu(II)-catalyzed

asymmetric Henry reaction 378CDC reaction between allylic C-H

bonds 44Cu(OAc)2 207, 266methylenemalononitriles,

monohydration of 14Cu2O catalysis, amidation 218Cu-catalyzed C-O coupling of alcohol

with halide 417, 418Cu-catalyzed oxidative 117Cu/Fe-cocatalyzed 20CuCl catalysis, amidation 211, 215,

222CuCl2 211CuCN 203cumene 244CuO 211cupreine-catalyzed enantioselective

Henry reaction 387Cu procedure, cyanation 267, 270CuSO4 203CuSO4.5H2O–H-phosphonate 322cyanation

carbon and nitrogen from DMdimethyl 269–271

carbon from DM dimethyl 266–269carbon from DMF carbonyl

264–266reagent 335–336

cyclic aryl ethers 414cyclic saturated ketones 463cyclization, VR-mediated 247–248,

250, 252cycloaddition, DMF/DMAc 278cycloalkanes 496, 502cyclohexanone 206cycloisomerization 292cyclopropane 147

522 Index

dDABCO 211, 223DavePhos (2′-(dicyclohexylphosphino)-

N,N-dimethylbiphenyl-2-amine)472

DCON(CD3)2 290DCON(CH3)2 290DDQ 10, 44, 70decanal 207decarboxylative alkenylation 104–106dehalogenation 260dehydrogenative cross-coupling 223,

224, 236, 238density functional theory (DFT) 42,

88, 109, 152Dess–Martin Periodinane (DMP) 37diacetoxyiodo benzene (DIB) 92diamines 177diarylalkenyl propargylic compounds

428diastereoisomeric 994,5-diazafluorene derivatives 4524,7-diazaindole-3-carboxaldehyde 2481,1-diarylalkane 4321,2-diaryl allylic alcohols 366, 367diaryl diselenides 2261,1-diarylethenes 2582,4-diaryl-1,3,5-triazines 284dibenzo[b,e][1,4]diazepines 284dibenzyl diselenides 226dibenzyldisulfanes, amidation of 2191,3-dibromo-5,5-dimethylhydantoin

(DBDMH) 611,3-dicarbonyl compounds 70, 373dichlorocarbene reactions

with amines 154cycloaddition 147formation 146–154use of 146–154

1,2-dichloroethane 211, 213, 217dichloromethane reactions

ketones/esters 139with amines 136–139with nucleophilic carbon derivatives

139–141with nucleophilic sulphur 141–142with phosphines 135, 136

with post-transition metals 126–127with transition metals 127–135

dichlorotetrakis (DMSO) ruthenium(II)and [RuCl2(DMSO)4] 315

dicumyl peroxide (DCP) 496, 499dicyanobenzenes, monohydration of

15diethanolamine 202, 204diethyl ether 82, 85,

2052,3-dihydrofuran, 94diformylation, VR-mediated 253–254dihydrofurans 497

synthesis 70dihydroisobenzofurans 332,3-dihydro-1,4-phthalazinedione 229

-mediated formylation 230dihydropyran 94dihydropyrazoles 278dihydroquinoline 181dihydroquinolinones synthesis 692,9-di-isopropylphenanthroline 4891,3-diketone 4171,2-dimethoxyethane 85dimethylamine 206, 207, 219, 255, 260,

291amidation/thioamidation using 209carbon from 262

2-(dimethylamino)benzo[b]thiophenes209

dimethylamino-carbon moiety,amidation/thioamidation using231–233

3-(dimethylamino)-2-formylacrylonitrile278

2-(dimethylamino)oxazolidin-4-ones278

2-(dimethylamino)-2-oxoethyl5-bromo-2-hydroxybenzoates234

3-(dimethylamino)-3-phenylchroman-2,4-dione 208

4-(dimethylamino)pyridine 2353-(dimethylamino)-2-((trifluoromethyl)

sulfonyl)-2-enals 272dimethylammonium dimethyl

carbamate (DIMCARB) 168dimethylbenzylamine 200

Index 523

(dimethylcarbamoyl)lithium 221dimethylcarbamoyl moiety, amidation/

thioamidation using 219dimethyl ether 95dimethylformamide diethyl acetal 294dimethylformamide dimethyl acetal

294dimethyl sulfoxide (DMSO) 3, 4, 14,

41, 163, 168, 173, 267carbonylation reagent 320–321cyanation reagent 335–336dimsyl anion activation reagent

339–342formylation reagent 332–335hydroxylation reagent 318–320in organic synthesis 315Kornblum oxidation 317–318MeSMe group 324–326methylation reagent 332, 333Parikh–Doering oxidation 316–317Pfitzner–Moffatt oxidation 317,

318properties 316ring/bridge formation 336–339self-sorting reaction system

342–348SMe group 326–331SOMe group 331–332sulfonylation reagent 321–324Swern oxidation 316

dimethylthioacetamide 294dimethylthioformamide 2945,5-dimethyl thiazolidinium-

4-carboxylate (DMTC) 163dimsyl anion activation reagent

339–3421,2-dinitrobenzene 1761,4-dioxane 85, 95, 1171,1-diphenylethylene 2231,2-diphenylethyne 210(2-diphenylphosphoryl-3-iodo-4-

methoxy-phenyl) methanol 276diphenyl sulfide 2261,3-dipolar cycloaddition reaction 4direct organocatalytic enantioselective

formal C(sp2)-H alkylation 392

dirhodium tetrakis(S-(N-dodecyl-benzenesulfonyl)prolinate)(Rh2(S-DOSP)4) 500

diselenides 2372,2′-disulfanediyldianilines 237, 240disulfides 2372,6-di-tert-butyl-4-methylphenol 292di-tert-butyl peroxide (DTBP) 61, 63,

68, 69, 73, 89, 95, 97, 98, 112, 114,238, 467

di-tert-butyl peroxide (DTBP)-promoted α-alkylation 498

DMA 13, 64DMF/HN(CH2CH2OH)2 204domino reactions 223, 276, 282

e(E)-2-azachalcones 389electrochemistry 278electron-deficient methyl arenes 61electron-rich aryl halides 415electron-rich methyl arenes (Method II)

61electrophile 424–436

alkene 426–428alkynes 428–430amination 424–436aromatic system 432–435indole 430, 431Ritter reaction 435–436

electrophilic fluoro(methylsulfinyl)methane 337

electrospray ionization tandem massspectrometry 259

emiaminal 260enamines

amidination 242VR-mediated formylation of 247

enaminones 394enediyne-carboxylic acids 22enantiomerically pure tricyclic

bispidines 378enantiomeric excess(ee) 109enantioselective synthesis 2, 42enol carbamates 221enolic carbons, methylenation of

282–283

524 Index

enolizable carbonyl compounds 242enones, benzylation of 69–70enzyme-catalyzed

aldol reaction 161–167bile acids acetylation 186

1,6-enynes 30esterification reaction 403–411Et3SiH 294etherification of alcohol with C–H

418, 421ethers 404

α-C–H amination 92α-C–H bond 101, 109α-C–H hydroxyalkylation 107–108alkylation reactions 104–106alkynylation 106–107amidation of 211–216aminoalkylation 107–108arylmetal/arylboron 109–112C(sp3)–H 82–97C–C bond 117–118C=C bonds 98–104CDC reaction 82–97C–O bond 112–117decarboxylative alkenylation

104–106decarboxylative alkylation reactions

105defined 81DMF/DMAc 285formation 285

acetalization 294acetylation 285amidation and thioamidation

209–241amidination 241–242amination 200–209anhydride formation 286carbonyl from 260cyanation 264cycloaddition 278formylation and domino reactions

242–260hydrodeoxygenation 294hydrogen delivery 289insertion reactions 271methylenation 278

methylidynation 283substitution 286–289thionation 294

intermolecular carbenoid insertion109

oxidative alkenylation 85radical alkenylation 106–107transesterification 187

ethyl acetate 182–192amidation of 187–189nucleophilic addition 192pyridin-2-ones 192transesterification reaction 183–187

9-ethylcarbazole 243ethyl diazoacetate reaction 72ethyl 3-dimethylamino-2-

(triethylsilyloxy)acrylate 276ethylenediamine 202ethyl picolinate 2141-ethynyl-2-(vinyloxy)benzenes 28(E)-vinyl methyl sulfones 3226-exo-trig cyclization 29(E)-or (Z)-2-methylthio-1,4-diones

342

fFeCl3 207FeCl3/AgSbF6 catalytic system 434FeCl3 catalysis

amidation 223methylenation 278

FeIII/K2S2O8/DMF procedure 282Fe3O(BDC)3 catalyst 238ferroceniumboronic acid

hexafluoroantimonate salt 435FeSO4-mediated reductive

defunctionalization 290flavones 88–90fluoroarenes 356formamidinium 236formic acid 206formoxylation 259–260formoxy-trifluoromethylthiolation 259formyl moiety, amidation/thioamidation

using 227formylation

DMF/DMAc 242

Index 525

reagent 332–335VR-mediated 243, 247–248

3-formylchromones 247formylmethylenoxazolidine-5-ones

248Friedel–Crafts alkylation 49, 70Friedel–Crafts reaction 413, 430furocoumarins 7fused pyran structures 411

gγ-hydroxy alkenes, cycloisomerization

292GC-MS 290germanes 294glycine 113glycol dimethyl ether 85grapheme oxide (GO) 167, 180Grignard reaction 81, 111, 114Grignard reagents 256

reaction with DMF 205

h1-haloalkenes 249haloformylation 242

VR-mediated 249–253halogenation reactions 73–754H-chromen-4-one 329HCO2H 290HCON(CD3)2 2901,2-hdroalkylation 373Heck reaction 291hemiacetal 260Henry reaction 377heptanoyl chloride 210heteroarenes 453

amidation of 238–240VR-mediated formylation of 243

(hetero)aryl halides, amination of 200hetero-Diels–Alder reaction 42heteropolymolybdovanadic acid

(HPMV) 452high-throughput experimentation

(HTE) methods 480H(Me)CONMeCH2 moiety, amidation/

thioamidation using 233–241HMe2SiOSiMe2H 294

HN(CD3)2 290HNMe2 209, 215, 216, 218, 260, 290Hoffman isocyanide synthesis 154homoallyl and allyl alcohols 422homolytic aromatic substitution (HAS)

mechanism 475Horner–Wadsworth–Emmons (HWE)

reaction 11511H-pyrido[2,1-b]quinazolin-11-ones

263H2S 216HSiMe2OSiMe2OCH2NMe2 295hydantoins 345hydrazides 97hydridochloropalladium 274hydridopalladation, of alkenes 271hydridopalladium 290, 291hydroamidation, of alkenes 272hydrocarbamoylation, of alkenes 271,

272hydrodeoxygenation, DMF 294–295hydroformylation 258hydrogen atom incorporation 2–7hydrogen atom transfer (HAT) 91hydrogen delivery 291

DMF/DMAc 289–294hydrotrifluoromethylthiolation 2932-hydroxyacetophenone 2352-hydroxybenzaldehyde 234, 256hydroxybenzamides 212hydroxydimethylcarboxamides 2213-hydroxyflavone 2082-hydroxyflavanones 37hydroxylation reagent 318–320hydroxyl group incorporation 31–392-(hydroxymethyl)-phenols 246, 4272-hydroxy-1,10-phenanthroline 460hydroxyphosphinylation reaction 7, 88-hydroxyquinoline 222, 4172-and 3-hydroxy substituted

benzaldehydes 378hypervalent iodine reagent 461

iI2 catalysis, amidation 217I2-catalyzed Povarov-type reaction

345

526 Index

I2/K2CO3 260I2/NH3 264imidazole 92, 181, 207, 209, 219, 228,

230, 235, 271imidazo[1,2-α]pyridines 238imidazopyridines 41imides, amidation of 236–237imine 357

reactions 174, 276imine-enamine tautomerization 9iminium 206, 232, 244, 246, 255, 259,

262, 266, 279, 281, 283, 288indanones 33indole 89, 92, 114, 238, 243, 430, 431

cyanation of 269indoline derivatives 227industrially important aliphatic olefins

409insertion reactions, DMF/DMAc 271intramolecular trapping, of

Vilsmeir-type intermediates254–256

inverse-electron-demandAza-Diels–Alder (IEDDA) 18

iodine 260iodonium 288

ion 82-iodo-1-phenylethan-1-one 342ionic liquids (ILs) 405i-PrOH catalyst 34Ir catalysis

amidoalkylation 233substitution 288

[Ir(COD)Cl]2 and 2,6-diisopropyl-N-(2-pyridylmethylene)-aniline487

iridium 471iron-catalyzed

aerobic nitro-Mannich reaction 386aerobic oxidative 26oxidation 91, 100

isatin 166, 167, 178, 179isochromanones (𝛿-lactones) 370isocyanide 12, 1772-isocyano-5-methyl-1,1′-biphenyl

226isonitriles, amidation of 226

isoquinolines 89N-benzylation of 75–76

kKarstedt’s catalyst 294K2CO3 43, 201ketene-N,S-acetals 248ketoacetophenone 217keto-enol tautomerism 12ketones 83, 84, 99, 100, 104, 112, 113,

184aldol reaction 162amidation of 221, 234–235amination of 206, 207Brøsted acid 161Mannich reactions 171, 174

KI 236kinetic isotope effect (KIE) 83, 499Knoevenagel condensation 176,

177KOH 201, 214

-mediated hydrolysis of DMF 290Kornblum oxidation 317–318K3PO4⋅ 3H2O 39K2S2O8 87, 293(-)-kumausallene 411

llactam carboxylic acid 253lanthanum(III) 184, 186Lewis acid 7, 14, 18, 19, 27, 32, 37, 42,

44, 69, 88, 102, 108, 113, 114,117, 272, 273, 289

Lewis acid (AgI/NiII/FeII)-catalyzed,Cu(II)-mediated thiolationreaction 327

Lewis acid and metal catalysis 436Lewis acid-Brønsted base

dual-activation approach 381Lewis-acidic catalyst 492ligand-assisted cyclopalladation

453LiHMDS 192LiH/MeCN 203lithium diisopropylamide (LDA) 191,

221long chain aliphatic alcohols 405

Index 527

long-chain surfactant-type Brønstedacid dodecylbenzenesulfonicacid 431

L-proline 161adol reaction 166amino alcohol 163enones and cyclohexanones 171in ionic liquid 178Mannich reaction 172organocatalysis 168

luminescent platinum(IV) 1272,6-lutidine 233

mmacrocyclic aromatic pyridone

pentamer 476malic acid production 411malonitrile 180malononitriles 15Mannich reaction 140, 170–175Markovnikov-regioselective

alkoxycarbonylation reaction409

Markovnikov’s rule 34Me3SiCl 205Me2SO4 294Meerwein arylation reaction 37Meerwein–Ponndorf–Verley reduction

175Meldrum’s acid 325-membered and 6-membered

N-containing heterocycles 471MeOH 260MeONa 294mesitylcopper/(R)-DTBM-Segphos

precatalyst 390MeSMe group 324–326mesylate 286

etherification of 285metal promoted 1,2-akylarylation 368metal trifluoromethanesulfonates 470methanesulfonic acid 2713-methyl-3-amidoethyloxindole 240methylation reagent 332, 333methyl azarenes, methylenation of 278methyl benzoate ester 93methyldibenzylamine 200

2-methylbutan-2-ol 2392-methyl-1,3-dithiane 256methylenation, DMF/DMAc

278–283methylene groups, VR-mediated

formylation of 247methyl ester synthesis 405methyl/ethyl acetate 184methyl 2-fluorobenzoate 214methyl groups, VR-mediated

formylation of 247methyl 3-(2-hydroxyphenyl)propiolate

288methylidynation, DMF/DMAc

283–285methyl ketones, amidation of 217–2184-methylquinoline 2403-methylthio-4-arylmaleimides 3423-methylthiomethylindole derivative

formation 324methyltrioxorhenium(VII)-catalyzed

oxidative conversion ofaldehydes 405

Meyer–Schuster (M.S.) rearrangement19

Mg/I2/NH3 procedure, cyanation 265Michael reaction 388–391microwave-assisted

Pictet–Spengler-typeheterocyclizations 337

microwave irradiation (MWI) 260,289, 498

Minisci-type coupling 91Mo(CO)6-catalysis, hydrodeoxygenation

294MOF-Cu(bcmim)2 212monodentate phosphine ligand 415multicomponent reaction 393multifunctional catalyst/reagent 342,

348

nN-acetylindoles 451Na2CO3 208NaH 276, 278NaI catalysis, amidination 241N-alkoxyamides 93

528 Index

N-alkyl-2-aminobenzophenones 51N-alkyl-N-alkoxyamides 93N-alkyl-N-methacryloyl benzamides

100N-alkylindoles 4511,8-naphthalenediaminatoborane

(HBDan) 487N-aroyl sufoximines synthesis 54–55N-aryl β-amino alcohols 35N-aryl-𝛾-lactam carboxylic acids 253N-aryl imines 26N-aryl-5-halo-pyrrole-

2,4-dicarbaldehydes 253N-aryl-2-picolinamides 225N-arylpyridin-2-amines 263N-arylpyrrolone 253Na2PdCl6 260naphthalen-1-ylmethyl acetate 206naphthalene 244Na2S2O3 209Na2S2O8 233, 456N-benzylformamide 206N-benzyl-4-methylaniline 219N-benzyl-4-methylbenzamide

219N-chlorosulfoximine, 54N-(diphenylphosphinoyl)propargyl

amines 21N-fluorobenzene sulphonamide (NFSI)

63N-fluorobenzenesulfonimide (NFBS)

465NH4HCO3 266, 269N-((hetero)benzyl)-N-methyl-

acetamides 238N-((hetero)benzyl)-N-methyl-

formamides 238N-heterocyclic carbene (NHC) 20, 133NH4I 267N-hydroxyphthalimide (NHPI) 52, 60,

99Ni/AlMe3 272, 273Ni0 catalysis, amidation 220Ni(acac)2-catalyzed 92Ni-catalyzed C–O coupling of alcohol

with halide 418, 419nickel 272, 289nickel catalyst 93

nickel(II) catalyst 141nickel-catalyzed regioselective 88nickel/copper synergistic catalysis,

carbonylation 262N-iodoimine 264nitrile

amidation of 218–219, 225–226cyclization 13free radical initiated C–H

functionalization 366–373hydration process 14insertion reactions 278transition metal catalyzed cross

coupling 355–366synthesis 60–61nitroaldol products,

381nitroalkenes 3833-nitro-2-arylimidazo[1,2-α] pyridines

3934-nitrobenzaldehyde 2112-nitrobenzoic acids 327nitro-containing compounds 383nitrogen

from DM dimethyl 269heterocycles 68ligands 486

nitromethanealuminium(III) chloride-catalyzed

three-component condensationreaction 393

Cu(OTf)2-catalyzed N-nitrosation394

direct cyanation 394direct organocatalytic

enantioselective formal C(sp2)-Halkylation 392

Henry reaction 377iodine catalyzed one-pot

four-component synthesis 393metal-free procedure 394Michael reaction 388–391multicomponent reaction 393N-Nitrosamine derivatives 394one-pot three-component reaction

393

Index 529

palladium-catalyzedcarbonation-diketonization392

reactions with aldehydes 377–384reactions with imines 385–386reactions with ketones 387–388tandem cross-coupling/𝜋-alkylation

procedure 392two-carbon homologation 392

2-nitrophenol 2222-(4-nitrophenyl)acetic acid 2113-nitropyridine 451nitro substituted oxindoles 369NMe2 283(N-methylacetamido)methyl benzoate

235(N-methylformamido)methyl benzoate

211, 235N-methyl formanilide 199N-methylindole 266, 267N-methyl-N-(3-oxo-3-arylpropyl)

acetamides 237N-methyl-N-(3-oxo-3-arylpropyl)

formamides 237N-methyl-N-(phenylthiomethyl)

formamide 226N-methyl-N-arylmethacrylamides

240N-methyl-N-phenylmethacrylamide

240N,N-bis(2-hydroxyethyl)formamide

204N,N-bis(silyl) enamines 242N,N-dialkylanilines 85N,N-dimethylthioamide 218, 219, 225N,N-dimethylthiobenzamide 215, 225N,N-dimethylacetamide (DMAc) 199

acetylation 285amidation and thioamidation

209–241amidination 241–242amination 200–209anhydride formation 286cyanation 264cycloaddition 278ether formation 285

formylation and domino reactions242

hydrogen delivery 289insertion reactions 271methylenation 278methylidynation 283substitution 286–289thionation 294

N,N-dimethylamides 211N,N-dimethyl aromatic amides 260N,N-dimethyl-2-arylethanethioamides

215N,N-dimethyl aryl thioamides 219N,N-dimethylbenzamide 210, 218,

219, 225N,N-dimethylbenzothioamide 217N,N-dimethylcarbamoyl chloride 242N,N-dimethylcyclohexylamine 206N,N-dimethyldec-1-en-1-amine 207N,N-dimethyldecan-1-amine 207N,N-dimethyl-1,1-diphenyl-

methanamines 205N,N-dimethylhex-1-en-1-amine 205N,N ′-dimethylethylene diamine 474N,N-dimethylformamide (DMF) 163,

199N,N-dimethyl-2-oxo-2-arylacetamides

217N,N-dimethyl-2-phenyl-2-(pyridin-2-yl)

ethanamine 279N,N ’-dioxide-Sc(OTf)3 391N,N,4-trimethylbenzamide 219N-nitrosoanilines 51N-nitrosamine derivatives 3941-nonene 207norbornene 272N-phenyl-N-(phenylsulfonyl)-

methacrylamides 496N-phenylpyridin-2-amines 261N-(pyridin-2-yl)arylamides 225N-phenylpyrimidin-2-amine 263N-substituted formamides 54N-sulfonyl formamidines 241N-sulfonyl-1,2,3-triazoles 9N-trifluoromethylthiodibenzene-

sulfonimide 259

530 Index

oO2 218o-(1-alkynyl)benzamides 36o-benzenedisulfonimide 435O-formates 246o-hydroxyacetophenones 247olefinic amides 372olefins 102o-methyl group, steric effect of 53O-nucleophile

Cu-catalyzed C–O coupling ofalcohol with halide 417, 418

esterification reaction 403–411etherification of alcohol with C–H

418, 421Ni-catalyzed C–O coupling of alcohol

with halide 418, 419Oxa-Michael addition 411–414Pd-catalyzed C–O coupling with

halide 414, 416O-phenylcarbamates 453o-phenylenediamine 176O(POCl2)2 242organic (pseudo)halides 477organobismuth perfluoro-

octanesulfonate (OBPFOS) 168organocatalysts 382organolithiens 256–258, 265organomagnesiens 256–258, 265organometallic agents 114organometallic reagents 114ortho-arylations 453ortho-hydroxyacetophenones 2821,3,4-oxadiazoles, amination of 207O-silylated ethers, VR-mediated

formylation of 246Oxa-Michael addition 411–414oxazines 253oxazoline 457oxazolo[4,5-b]pyridine 207oxidation of alcohols 421, 422oxidative alkenylation reaction 85oximes 95, 96oxindoles syntheis 68–692-oxo-2-arylacetic acids 213oxonium 2462-oxo-2-phenylacetic acid 235

oxygen atom incorporation 7–301,2-oyalkylation 370

pP2O5 211palladium (Pd) 230, 266, 270–272,

290palladium catalysis

amidation 214, 219carbonylation 209, 260, 261

amidation 231, 234amination 209cyanation 269hydrogen delivery 290, 291cyanation 269

palladium-catalyzed 97, 116carbonation-diketonization 392carbonylative α-arylation to

β-ketonitriles 362C–O coupling of alcohol with halide

414, 416C(sp3)–H hydroxylation 38cyanation 266decarboxylative coupling of

cyanoacetate salts 357direct arylation of naphthalene 450R-arylation of nitriles 358site-selective cyanomethylation

363palladium/copper-catalyzed 87palladium hydride 291[2.2]paracyclophane 293[2.2]paracyclophane-based bis(thiourea)

catalyst 382Parikh–Doering oxidation 316–317PBr3 242Pd(dba)2 459Pd(II)-catalyzed

aldehyde-selective 10allylic C–H bond 11cross coupling reaction 51enediynes, bimolecular

carbocyclizations of 22, 23hydrogen acceptor and two-electron

oxidant 10nitrile-directed C-H activation 13ortho-trifluoromethylation 43

Index 531

Pd(OAc)2 266, 267, 453Pd(OAc)2/AgOTf synergistic catalysis,

carbolynation 263Pd(OAc)2/bpy catalytic system,

amidation 230PdCl2 260, 266, 267PdCl2-WCl6 catalysis, amidation 231Pd/C-POCl3 catalysis, amidation 231Pd/Cu-catalyzed enediyne,

intermolecular cyclization of23

Pd/Cu procedure, cyanation 266Pd/PhCOCl 272, 273PdX2/N-phenylpyrrole phosphine 409pentylmagnesium bromide 205per-6-amino-β-cyclodextrin 382peresters, amidation of 211–216perfluorinated arenes 453peroxides 240peroxydes 237peroxydisulfate 239Pfitzner–Moffatt oxidation 317, 318phase transfer catalyst (PTC) 74Ph3SiOSiPh3 294PhCH(Bpin)2 485PhCO2CONMe2 211PhCO2H 207, 211, 218PhCOCl 242PhCO3t-Bu 211PhCONMe2 211phenanthridinone derivatives 4801,10-phenanthroline 218phenethyl 2-methylbutyrate 410phenols

amidation of 221–223VR-mediated formylation of

246–247phenylacetic acids 2152-phenyl acetic acid synthesis 61–62phenylacetonitriles 2252-phenylacetyl chloride 210phenylacetylene 250phenyl-1,3-butadiene 223, 2724-phenylbut-3-ene-2-thione 3361-phenylethyl acetate 458phenylglyoxal 347phenyliodonium diacetate (PIDA) 60

2-phenylpyridines 453, 4571-phenylpyrrole 2852-(1-phenylvinyl)pyridine 279PhMeSiH2 295phosphate esters synthesis 66phosphine ligands 486phosphorus oxychloride 199photoredox catalysis 15photosensitizer 290phthalide 260phthalide (𝛾-lactones) 370piperazines 42pivalic acid 230platinium(IV) 127p-methoxyphenylprop-1-en-3-one

283, 289POBr3 242POCl3 242, 243, 246, 250, 256, 264,

285poly-(diallyldimethyl ammonium)

hexafluorophosphate 166polycyclic aromatic compounds,

perdeuteration of 289polycyclic polyprenylated

acylphloroglucinols (PPAPs) 15poly tetraflurorethylene (PTFE) 142potassium carbonate 217, 218, 225potassium persulfate 226, 239potassium persulfate (K2S2O8) 261Povarov reaction 85PPh3⋅HBr–DMSO-mediated oxidative

bromination 344primary alcohols

amidation of 216–217amidoalkylation of 238

privileged chiral ligands 380proazaphosphatrane catalyst 412proline-catalyzed, aldol reaction 162prolinol-based catalysts 390propiolamides 223, 224proton-type ionic liquid ([Hmim]OTs)

413protonic acid catalyzed 113Pt(II)-catalyzed, oxo-alkyne-nitrile 21purine nucleosides 92pyran 95pyridine-N-oxides, benzylation of 70

532 Index

pyridine synthesis 181pyridinone 255pyridyl arenes, cyanation of 270pyrroles 248

synthesis 393pyrrolidine 83

qquinazoline 283, 336quinoline 71–72

N-oxides 90synthesis 181

quinone 465

rradical trapping 292reduced Knoevenagel adducts 365regioselective hydrocarbamoylation, of

alkenes 271Reimer–Tiemann reaction 150resin-supported peptide catalyst 390resorcinol 256Rh catalysis

amination 207hydroformylation 207hydrogen delivery 289methylenation 283

RhII catalysis, insertion reaction 277Rh(II)-catalyzed 31

denitrogenative hydration reaction9

Rh(OAc)2 catalysis, insertion reaction276

Rh-catalyzed 110dehydrogenative silylation of arenes

489oxidative alkenylation of arenes

464rhodium(I) 132rhodium carbene 276ring opening, VR-mediated 252–253Ritter reaction 435–436Rockphos 415(1R 2S)-2-amino-1,2-diphenylethanol

380R3SiCl 236Ru catalysis, amidoalkylation 233

Ru3(CO)12 catalysis, insertion reaction272

Ru(bpy)3Cl2 233RuH(CO)(PCy3)(C6H6)]BF4 catalyst

433ruthenium-catalyzed 21

aromatic nitriles cyclization 13intramolecular carbocyclization 22

ruthenium complex-catalyzed directaddition 356

sS8 215, 225salen-type C2-symmetric ligands 380salicylaldehydes 222Schmidt type rearrangement 60secondary homoallyl alcohol 422seimatopolide A 191selectfluor 8, 9, 17, 31, 32selenides 505

amidation of 226–227selenocarbamates 226self-sorting reaction system 342–348Shvo’s catalyst 34silanes 267, 294silicic acid 228silver(I)-catalyzed

alkynes hydroazidation 4ethynyl carbinols hydroazidation 3,

4TMS-N3 3, 4

silver phosphate 42silyl ether 246Singer’s Bippyphos ligand 415single electron transfer (SET) 12, 15,

60, 70, 73, 83, 239, 266, 479SMe group 326–331(S)-moprolol 380SN Ar of aryl fluorides 356(S)-N-trans-feruloyl octopamine 378SOCl2 211, 242sodium 258sodium amide 228sodium azide 493sodium diphenylbismythyl 126sodium ethoxide 294sodium hydride 228

Index 533

sodium methoxide 242sodium methylate 228solvothermal method 223SOMe group 331–332(-)-sparteine 256S-phenyl dimethylcarbamothioate 226(S)-proline catalysis 166, 174(S)-propanolol 380(S)-(-)-spirobrassinin 387Staudinger reaction 4, 5stilbene oxidation 8(S)-tolirolol 380styrenes 36, 223, 237

formoxy-trifluoromethylthiolation of259

styrylmethylketone 2183-substituted 3-hydroxyoxindoles 387substitution, DMF/DMAc 286sulfides, amidation of 226–227, 237sulfonamides 482

acetylation 189amidination 241–242

sulfonylation reagent 321–324sulfonyl-containing ammonium-based

Bronsted acid ionic liquid 430sulfoximines 504sulfur 215, 217, 218, 225sulfuric acid 228Swern oxidation 316synergistic catalysis, carbonylation

262, 263synergistic effect 10, 12synthetically accessible alkoxysilanes

490

ttandem reaction 91tautomer 178TBHP 16, 51, 54, 58, 64, 66, 85, 87, 89,

91, 95, 96, 98, 100, 102, 104, 106,108

t-BuCO2H 231t-BuOK 219, 289t-BuONO 26–28t-BuOOH 208, 211, 214, 216–218,

221, 224–226, 235, 236, 240, 241t-BuOO 216

t-BuOOt-Bu 212, 223t-butyl benzoperoxoate 211t-butyldimethylsilyl chloride 235t-butyl perbenzoate 226t-butylperoxy benzoate (TBPB) 67, 69,

467Teflon AF-2400 membrane tube-in-tube

reactor 386tert-butyl nitrite (TBN) 25, 28, 29, 60tetrabutylammonium iodide (TBAI)

54, 66, 92, 1043,4,5-tetrafluorophenylboronic acid

catalyzed direct Friedel–Craftsalkylations 433

tetraflurorethylene (TFE) 142tetrahydro-2H-thiopyran 85tetrahydropyranyl (THP) ether 83, 85,

93tetrahydrothiophene 851,1,3,3-tetramethylguanidine (TMG)

1752,2,6,6-tetramethyl-1-piperidine-1-oxyl

(TEMPO) 22, 27, 85, 87, 292,371

2,2,6,6-tetramethyl-1-piperidinyloxy236

tetramethyl-1,10-phenanthroline 417tetrasubstituted olefins 460TFA 13, 35, 173TfOH-catalyzed domino

cycloisomerization/hydrolyticdefluorination reaction 8

THF 85, 95thiazoles 41thioaldehyde 215thioamidation, DMF/DMAc 209thioethers 97

synthesis 56thionation, DMF/DMAc 294thiophenols

alkylation of 63–64amidation of 223

three-component carboetherification372

Ti(Oi-Pr)4 205tin(II)chloride 126TMEDA 137

534 Index

toluene 244amides synthesis 53–54benzo[b]phosphole oxide synthesis

72–733-benzyl coumarins 66–67benzyl esters 64–65β-aromatic α-amino acids 73carbamates synthesis 66carbonyl compounds, synthesis of

51–53dihydrofurans synthesis 70–71dihydroquinolinones synthesis 69direct esterification 55enones, benzylation of 69–70esters synthesis 55–56, 66esthers, application 76–77ethyl diazoacetate reaction 72halogenation reactions 73–75methyl group, application of 51–59methyl group, oxidation of 50–51N-aroyl sufoximines synthesis

54–55nitriles synthesis 60–61oxindoles syntheis 68–692-phenyl acetic acid synthesis

61–62phosphate esters synthesis 66physical properties 50pyridine-N-oxides, benzylation of

70quinoline 71–72thioamides synthesis 66thioesters synthesis 56–59thiophenols, alkylation of 63–64trifluoromethyl sulfides synthesis

64topoisomerase I inhibitor 76tosylate 286

etherification of 285tosylation 259transamidation 271transition-metal catalysts,

hydrodeoxygenation 295transition-metal-free conditions 871,3,5-triazines 2841,2,3-triazoles 2771,2,3-triazolyl pyrazole 248

2,4,6-trichloro-1,3,5-triazine (TCT)176

triethylamine 235, 276triethylbenzylammonium chloride

(TEBAC) 148triethyloxonium fluoroborate 294triflates

amidation of 209carbonylation of 209

triflic anhydride 259trifluoroacetic acid 261trifluoromethanesulfonic acid 64trifluoromethyl ketimines 173trifluoromethyl sulfides synthesis 64tri(iso-propyl)silyl triflate 276trimethylamine 294, 295trimethylsilylacetonitrile 3622-(trimethylsilyl)aryl triflate 12trimethylsilyl azide (TMS-N3) 3trimethylsilyl chloride 2351,3,5-trimetylbenzene 244triphenylphosphine (TPP) 5triphenylphosphinecarboxamide (TPPc)

5, 6triphenylsilanethiol 2942,4,5-trisubstituted furans 329TsOH 218Tsuji–Trost reaction 205

uumbelliferone synthesis 256unactivated aryl chlorides 474unactivated C(sp3)-H bonds 363unusual peroxide-mediated amination

502

vvaleraldehyde 218, 225Verapamil 361Vilsmeier salts 232Vilsmeier-type reagents (VRs) 199,

242, 243cyanation 264-mediated domino reactions

247–256-mediated formylation 243–247role in acetylation 285

Index 535

vinylarenes 424vinyl bromides 291vinylcyanides 267vinyl epoxide reaction 149vinyl halide 150vinyl iodides, carbonylation of 2091-vinylpyrroles 243vinylsilanes 267visible light reaction 233, 290visible-light promoted 1,2-akylarylation

369VIV/PhI(OAc)2/DMF procedure 281

wWacker oxidation 9, 10, 24water

catalyst-free sulfonylation 2, 3hydrogen atom incorporation 2–7hydroxyl group incorporation

31–39oxygen atom incorporation 7–30

Wilgerodt–Kindler type rearrangement216

xXylenes

amides synthesis 53–54β-aromatic α-amino acids 73benzo[b]phosphole oxide synthesis

72–733-benzyl coumarins 66–67benzyl esters 64–65

carbonyl compounds, synthesis of51–53

dihydrofurans synthesis 70–71dihydroquinolinones synthesis 69enones, benzylation of 69–70esters synthesis 55–56, 66ethyl diazoacetate reaction 72halogenation reactions 73–75methyl group, application of 51–59methyl group, oxidation of 50–51N-aroyl sufoximines synthesis

54–55nitriles synthesis 60–61oxindoles syntheis 68–692-phenyl acetic acid synthesis

61–62phosphate esters synthesis 66physical properties 50pyridine-N-oxides, benzylation of

70quinoline 71–72thioamides synthesis 66thioesters synthesis 56–59trifluoromethyl sulfides synthesis

64

z(Z)-crotyltrichlorosilane 278zinc cyanoalkyl reagents 361zinc dust 286zirconium oxide 228zwitterion 277