Index

acetal exchange 126, 136, 154, 160, 293,316, 566

acetalisation 59–60, 64N,N-acetals 98, 369–371, 388N,O-acetals 96–99, 173–179, 232,

561–568, 626–630O,O-acetals 5–7, 11, 50–77, 101, 120–160,

285–320, 342, 426–430acetamidomethyl 372, 381, 384acetate esters 3, 168, 206, 325, 334, 338acetate migration 196, 33680% acetic acid 595acetic acid 5–6, 139–140, 156, 175–176,

190, 196, 200, 208, 216, 265, 269, 315,318, 341, 343, 461, 529, 564–565, 582

acetic acid in ether 599acetic acid in refluxing 2-propanol 404acetic anhydride 156, 238, 298, 323, 497,

559acetonides 202a-acetoxy 92p-acetoxybenzyloxycarbonyl (AcOZ) group

518acetoxymethyl acetal 156acetoxymethyl ether 1572-(acetoxymethyl)benzamides 501N-acetyl neuraminic acid 4, 177, 258, 3302-acetyldimedone 606acetylene 490acetylenes 411acid and moisture sensitivity 595acidic exchange resin 287Acivicin 505, 513ACRL toxin IIIb 270Actinobolin 548Actinoidic Acid 108acyl anion equivalents 78, 99, 106acyl migration 217, 265, 330, 479N-acylaminal 536N-acylaziridine 1092-acyl-1,3-dithiane 91, 96, 2701-adamantyloxycarbonyl (Adoc) 6141,2-additions 32adenine 620Adenophostin A 481

N-adenylated S-methyl-l-cysteine sulfox-imine 516

Agelastatin A 508, 555Agrocin 84 477AI-77-B 576alanine 552Albomycin 595aldol reaction, directed 26alkene 516alkenes, terminal 55O-alkyl nucleophilic scission 399alkylammonium formate 467alkylation 39, 87, 94, 370alkylation, asymmetric 411S-alkylation 7alkyllithium reagents 137allene 70Allopumiliotoxin 339A 245Allosamidin 557allyl alcohol 606allyl bromide 595allyl carbamate 39allyl chloroformate 284, 346, 423, 528allyl esters 12, 37, 422, 517, 526allyl ethers 12–13, 39, 246, 276, 278, 422allyl isopropenyl dicarbonate 423p-allyl palladium 12, 418, 422, 594–595,

606–607allyl phosphates 467allyl scavengers 387allyl 2,2,2-trichloroacetimidate 423allylamines 593–594allylic amination 555allylic p-methoxybenzyl ether 261allylic TBS ether 212allyloxycarbonyl (Aloc) 345–347, 436, 468,

540, 575, 625N-allyloxycarbonyl (N-Aloc) 37, 39, 419,

524–528allyloxycarbonyl group selectively iso-

merised using Pd or Rh catalysts 278allyloxycarbonylaminomethyl 385allyltrimethylsilane-trifluoroborane 568Alterobactin A 430, 617Altohyrtin C 333

Protecting Groups Third Edition by Philip J. Kocieński Protecting Groups Third Edition by Philip J. Kocieński

Protecting Groups Third Edition by Philip J. Kocieński

alumina 58, 241aluminium amalgam 548, 553Amamistatin A 312Amberlyst 58, 59, 174, 269, 320Ambruticin 399amide hydrolysis 4amides 16, 510amidines 620amination 20amines 8–9, 14, 586, 597amines, primary, asymmetric synthesis 584p-aminobenzyl 20, 341aminoglycoside antibiotics 5592-amino-2-methyl-1-propanol 109, 546, 592ammonia 3, 326, 375, 467, 471, 529, 603,

620ammonia equivalent tert-butyl 2-(trimethyl-

silyl)ethylsulfonylcarbamate 557ammonia in methanol 336, 625ammonia in toluene 336ammonia, liquid 11, 245, 543ammonium bifluoride 207ammonium fluoride 171, 206ammonium formate 9, 242, 516, 530ammonium hydroxide 171Amphidinolide L 311tert-amyl 240(–)-Ancistrocladine 5842,5-anhydro-2,5-imino-d-glucitol 573anisaldehyde 584anisaldehyde dimethylacetal 150anisole 367–368, 404, 410, 414, 506, 548,

587p-anisyloxymethyl 306anomeric effects 161anomeric thiol 380anomerisation 17anthranilic acid 482N-9-anthrylsulfonyl 547–548Antibiotic 593A 514Antibiotic 1233A 124, 131Antibiotic X-206 302, 304Anticapsin 396Antillatoxin 527Antrimycin 419Aphidicolin 90Aplasmomycin 290Aplyronine A 212, 306Aplyronines 321Apoptolidine 258, 277d-(+)-arabitol 154

Arachidonic Acid 75arginine 250, 610, 613, 617–618arginines, monoprotected 610Ascomycin 629asparagine 524, 585aspartic acid 371, 458, 590Asperazine 342, 625Aspergillus niger lipase (ANL) 329Aspicillin 32, 166Aspirochlorine 388atropisomers 107Avermectins 294, 347aza-crown ethers 546Azadirachtin 87, 254azeotropic distillation 58–59azides 278, 496azido groups 4114-azidobenzyloxycarbonyl 6124-azido-1,1,1-trimethoxybutane 332, 607Azinomycin 586Azinomycin A 516aziridine 516aziridinomitosene 532azobis(isobutyronitrile) 370, 560

Baccatin III 176, 566Bactobolin 554Bafilomycin A 210Bafilomycin A1 224Balanol 406Bao Gong Teng A 570barbituric acid 12barium carbonate 79barium hydroxide 503barium hydroxide octahydrate 266, 397barium oxide 266Bartanol 428basicity 208Batrachotoxinin A 63, 86Baudry’s catalyst (Ir(COD)[PMePh2]2PF6

276–2779-BBN 168benzaldehyde 150, 153, 584benzaldehyde dimethyl acetal 150, 1541,2-benzenedimethanol 55o-benzenedisulfonyl chloride 267benzeneselenol 64benzenethiol 234, 265, 304, 367, 458, 464,

548, 553benzenethiol and triethylamine 458benzhydrylamines 573

658 Index

Protecting Groups Third Edition by Philip J. Kocieński

benzoate esters 3, 57, 147–148, 326, 330,334, 338, 491, 532

1,3-benzodithiolan-2-yl (BDT) ether 1261,3-benzodithiolanyl tetrafluoroborate 126benzoin 14benzopentathiepine 367benzophenone dimethyl acetal 160benzophenone hydrazone 416benzophenone imine 601benzoquinone 66benzostabase 598–599benzothiazole-2-sulfonyl 553benzothiazole-2-sulfonyl chloride 552benzoyl 258, 330–331N-benzoylphenylisoserine 566N-benzyl 411, 570–585benzyl alcohol 522benzyl 1,2,3-benzotriazole-1-carboxylate

523benzyl bromide 253benzyl bromomethyl ether 304benzyl chloroformate 379, 415, 522, 613benzyl chloromethyl ether 304benzyl esters 5, 232, 242, 289, 398,

409–417, 443, 506, 512–513, 528,530–531, 612

benzyl esters reduced without harm tosome Cbz groups or benzyl ethers 515

benzyl ethers 9, 11, 22, 32, 158, 173, 178,242, 290–291, 300, 411, 481, 506, 512,572, 588, 601

benzyl hydroxamates 244benzyl isocyanate 576benzyl phosphate esters 411, 464benzyl 2,2,2-trichloroacetimidate 256, 415N-benzylation 2562-benzyl-1,3-dithiane 79, 226, 367–369,

373, 505, 575–577, 579, 584, 606benzylic carbanions, dipole stabilised 579benzylidenation 154benzylidene acetals 11, 137–155, 168, 216,

227, 242, 252, 257, 309b-benzyloxy aldehydes 32benzyloxycarbamates 411benzyloxycarbonates 411benzyloxycarbonyl (Cbz or Z) 9, 37, 174,

238, 242, 290, 300, 339–341, 506,512–524, 528, 536, 540, 610–618, 625

(S)-2-(benzyloxycarbonylamino)succinicacid 4-methyl ester 103

N-(benzyloxycarbonyloxy)succinimide 523

benzyloxymethyl 6, 258, 563–564,626–629

benzyloxymethyl (BOM) ethers 61, 301–305, 411, 572

(R)-N-benzylphenylglycinol 97benzyltrimethylammonium cyanide 532benzyltrimethylammonium fluoride 207Bertyadionol 86bimolecular nucleophilic substitution 11(+)-Biotin 369Biphenomycin 247Biphenomycin A 514, 564Birch reduction 141, 245, 303, 4141,3-bis(diphenylphosphino)propane 66,

282, 594bis(2-cyanoethyl) N,N-diisopropylchloro-

phosphoramidite 474bis(ethylthio) acetal 81bis(9-fluorenylmethyl)-N,N-diisopropyl-

phosphoramidite 475bis(methoxyphenyl)methanol 582bis(4-methoxyphenyl)methyl 581bis(2-oxooxazolidin-3-yl)phosphinic chlor-

ide 6053a,3a0-bispyrrolidinoindoline alkaloids 574bis(2-thienyl)ditelluride 541Bistratamide D 515bis(tributyltin) oxide 255, 397, 407, 425[bis(trifluoroacetoxy)iodo]benzene 84, 91,

161, 163, 500, 598–599, 612–614, 6161,2-bis(trimethylsilyloxy)ethane 61, 63, 70,

127bis(trimethylsilyl) sulfate 319borane 120borane in THF 145borane-amine complex 526borane-diethylamine complex 527borane-dimethylsulfide complex 143borane-trimethylamine complex 143, 145boric acid on silica 270Boromycin 148boron trifluoride etherate 408, 415Brefeldin 320, 418Brevetoxin 101Brevetoxin A 81, 141Breynolide 276bromine 68, 81a-bromo acetal 68, 252, 590p-bromobenzoate esters 326p-bromobenzyl ether 21B-bromocatecholborane 290, 300, 304, 508

Index 659Protecting Groups Third Edition by Philip J. Kocieński

bromodi(isopropylthio)borane 290bromodimethylborane 21, 54, 76, 124, 216,

265, 291, 299, 309, 508bromodiphenylborane 2992-bromoethanol 65bromoetherification 232-bromoethyl ester 432bromohydrin 23bromomethyl methyl ether 2932-bromomethylbenzoate esters 21N-bromosuccinimide 7, 82, 137, 148, 548bromotrichloromethane 149bromotrimethylsilane 166, 288, 367, 460,

462, 513bromotrimethylsilane in trifluoroacetic

acid, containing thioanisole 513Bryostatin 198, 260, 411Bryostatin 2 334Bryostatin 3 419Buphanasine 526(R,R)-(–)-butane-2,3-diol 67, 103, 154butane-2,3-dione 165butanethiol and potassium carbonate in

conjunction with magnesium bromide inether 309

butane-1,2,4-triols 130, 1533-O-butanoyl-d-glucose 329–330(Z)-2-butenol 490butenolides 1061-(tert-butoxy)-1,2-benzoiodoxol-3(1H)-

one 251tert-butoxycarbonyl (Boc) 35, 211, 237,

290, 300, 326, 404, 428, 616N-tert-butoxycarbonyl 16, 76, 232, 289,

366, 369, 378–379, 382, 385, 424, 436,506, 510, 538, 540, 552, 557, 606–607,614, 616–617, 625, 628

2-(tert-butoxycarbonyloxyimino)-2-phenyl-acetonitrile 510

tert-butyl ethers 5, 37, 51, 148, 169, 211,237–241, 282, 290, 295, 300, 313, 326,341–342, 366, 368, 373, 376, 378–379,382, 384–385, 403–404, 407–409, 415,458, 460, 478, 506–507, 510–512,528–529, 541, 556–558, 561, 568, 599, 603

tert-butyl mercaptan 380butylammonium formate 469butylammonium formate and Pd(0) 468tert-butylcarbamates 123tert-butyldimethylsilane 229, 443tert-butyldimethylsilanol 215

tert-butyldimethylsilyl (TBS) 7, 22, 32, 35,53–55, 57, 86, 88, 122–124, 140, 147,158, 166, 168–169, 177, 191–192,195–198, 199–216, 218–220, 223, 225,242, 258, 288, 316, 335, 405, 429, 437,440–444, 460, 465, 499, 506–507, 509,536, 555, 596–597, 618, 623

tert-butyldimethylsilyl ethers 122, 218, 221,269–270, 290, 295, 298, 300

tert-butyldimethylsilyl triflate 213, 240tert-butyldiphenylsilyl (TBDPS) 7, 202,

206, 209, 216–220, 242, 260, 288, 312,335, 440–444, 458, 595

tert-butyldiphenylsilyl ethers 31–32, 53,122, 144, 197, 200, 219, 329, 433, 441,478, 506, 595

tert-butyldiphenylsilylamines 5952-[(tert-butyldiphenylsilyloxy)methyl]ben-

zamides 501tert-butyllithium 35, 168–169, 199, 579tert-butylmagnesium chloride 314tert-butylmethylidene acetals 147S-(tert-butylsulfanyl)cysteine 380, 384butyrylcholine esterase 19

C NMR spectroscopy 132cadaverine 606cadmium carbonate 79, 321cadmium in DMF–HOAc 431cadmium–lead couple 540, 541calcium carbonate 79, 81, 321calcium in liquid ammonia 271calcium sulfate 58Calicheamicin g1

I 252Calicheamicin–Dynemicin 529Calicheamicin–Esperamicin 25Calicheamicinone 306Calicheamicinone g1I 535Callipeltose 174Calphostin A 232Calyculin 31, 260Calyculin A 205, 224, 465, 473, 476camphorsulfonic acid (CSA) 53, 58, 126,

150, 163–164, 168, 176, 257, 316, 319,326, 567

Candida cylindracea lipase (CCL) 329carbamates 9, 12, 412carbon disulfide 599carbonates 121,2-carbonyl transposition 92carbonyldiimidazole 345

660 Index

Protecting Groups Third Edition by Philip J. Kocieński

carboxamidomethyl (CAM) 379, 425N-carboxyanhydrides 585carboxylate anion 11carboxylic acids 7, 11, 14, 16carboxylic esters 57Carnosidine 489castanospermine 328catalyst poisoning 241, 411catalytic hydrogenation 51, 141, 514, 601catalytic hydrogenolysis 264, 301, 410, 414catalytic transfer hydrogenation 411, 572catalytic transfer hydrogenolysis 302catechols 158Cephalosporin C 430Cephalosporins 416Cephalotaxine 101cerebrosides 174cerium(III) chloride 77cerium(III) chloride and sodium iodide 283cerium(III) chloride heptahydrate 54cerium(III) chloride heptahydrate together

with sodium iodide 265cerium(IV) 84cerium(IV) ammonium nitrate (CAN) 11,

55, 84, 149, 263, 316, 509, 572, 575,578–579, 581

cerium(IV) ammonium nitrate absorbedon silica 270

cesium benzenethiolate 399cesium carbonate 253, 402cesium carboxylates 402cesium fluoride 254, 310, 537, 554, 557Cetirizine hydrochloride 546Chaenorhine 607charge transfer 15charge transfer complex 134chelation control 32chelation-controlled addition 94chiral acetal 70chiral ammonia equivalent 592chiral auxiliary 96Chlamydocin 64chloramine T 83chloride as nucleophile 12chlorine 81N-chloro-p-toluenesulfonamide, sodium

salt 83, 299, 435, 494a-chloroacetamide 425chloroacetate esters 3, 196, 335–338, 475chloroacetic acid 191chloroacetyl 233

p-chlorobenzyl ether 214-chlorobutanamides 5022-chlorocarbonylbenzoic acid methyl ester

493chlorocarbonylsulfenyl chloride 497chloro-di-tert-butylsilane 170chlorodiethylalane 147chlorodiethylalane/triethylsilane 153chloro(diisopropylamino)methoxypho-

sphine 457chloro-di-isopropylsilane 170chlorodimethylalane 124, 563chlorodimethylsulfonium chloride 4292-chloroethyl acetal 19chloromethyl methyl ether 292, 307, 563chloromethyl methyl sulfide 322, 429chloromethyl 2,2,2-trichloroethyl ether and

potassium hydride 564m-chloroperbenzoic acid 65, 864-chlorophenol 5072-chlorophenyl phosphate 469N-chlorosuccinimide 82, 84Chlorotetaine 401Chlorothricolide 61, 74, 216, 309, 421chlorotriethylsilane 198chlorotrimethylsilane 54, 60, 65, 72, 90,

145, 192, 289, 332, 401, 435, 461, 4732-chlorotrityl 37choline esters 17, 19Chromobacterium viscosum lipase 329chymotrypsin 330citric acid 109Clavalamine 414Clavicipitic Acid 624S,S-cleavage 367, 468cobalt(I) phthalocyanine 432, 5412,4,6-collidine 82, 322, 324, 341Concanamycin 397Concanamycin F 210, 224conjugate addition 33–34, 39, 65–66,

98–100, 106, 153, 373Conotoxin G1 384Conotoxin M1 384copper(II) 148, 614copper(II) chloride 88copper(II) chloride dihydrate 123copper(II) oxide 88copper(II) sulfate 58, 126, 269Coriarin A 158Cortisone 63CP-262,114 86

Index 661

Protecting Groups Third Edition by Philip J. Kocieński

CP-263,114 292Crambescidin 59o-cresol 247, 368, 460Crinine 526Crispatine 289Cristatic acid 311crotyl ether 28118-crown-6 100, 218Cryptophycins 1 and 8 332cumene 15Curtius rearrangement 534, 536cyanide as nucleophile 12p-cyano ethers 252cyano group 9920-(cyanoethoxy)(N,N0-diisopropylamino)-

chlorophosphine 4712-cyanoethyl 375–376, 439, 473–475Cyclindrocyclophane A 234cyclisation, asymmetric tandem 70cyclisation to form a b-lactam 610[3+2]-cycloaddition on the alkene of the

allyl ether function 2781,4-cyclohexadiene 9, 242, 411, 516, 572cyclohexane-1,2-dione 164cis-cyclohexane-1,3,5-triol 103cyclohexanone 52, 135cyclohexene 9, 242cyclohexylidene acetals 126, 133–137, 175,

262cycloisodityrosine derivatives 395cyclopentanone 89, 135cyclopentanones 52cis-4-cyclopentene-1,3-diol 327cyclopentylidene acetals 126, 133–137,

272, 281, 336, 408Cyclophellitol 344cyclopropanation 67–68, 96, 99Cyclotheonamide 507Cyclotheonamide B 250, 614Cyclotheonamides A and B 490Cylindrospermopsin 565cysteine 368–369, 373, 376, 381, 511l-cystine 380cytidine-50-monophosphono-N-acetylneura-

minic acid (CMP-Neu5Ac) 468Cytoblastin 627Cytovaricin 168, 223

Dactomelynes 142Damavaricin 418, 537Damavaricin D 216

Daunomycinone 340deacetalisation 549-deazaguanine 620decarboxylation 411dehydration 55, 58–59, 61cis-9,10-dehydroepothilone D 203dehydrogenation 84Deltamethrin 96Denticulatins 1526-deoxy-D-gulal 757-deoxypancratistatin 287depurination 17Dess–Martin periodinane 168desymmetrisation 153, 166dethioacetalisation 78N,N0-dialkyl-O-methyl-isoureas 402diallyl dicarbonate 423, 5281,16-diamino-4,8,13-triazahexadecane 606di-(p-anisyl)methylene 160, 3071,4-diazabicyclo[2.2.2]octane (DABCO)

276, 4621,8-diazabicyclo[5.4.0]undec-7-ene (DBU)

57, 192, 267, 273, 375–376, 437, 439,473, 481, 529

9-diazofluorene 417diazomethane 237, 401Diazonamide 2521-diazo-2-propene 423dibenzocyclopentadienide anion 9dibenzofulvene 9dibenzosuberyl group 574dibenzoyl peroxide 323dibenzyl aspartate 596dibenzyl dicarbonate 415, 523dibenzylamine 621dibenzylformamide dimethylacetal 6211,2-di-O-benzyl-l-threitol 67, 1281,3-dibenzyl-1,3,5-triazinan-2-one 568, 620dibenzylurea 569diborane 2832,7-dibromo-9-phenylxanthen-9-yl 272, 5574,40-di-tert-butylbiphenyl 5464,40-di-tert-butylbiphenylide 246dibutylboron triflate 142di-tert-butyldichlorosilane 170dibutyldichlorostannane 324di-tert-butylmethylsilyl triflate 230, 441(R)-di-tert-butylphosphorylglycidol 4612,6-di-tert-butylpyridine 213, 236di-tert-butylsilyl bis(trifluoromethanesulfo-

nate) 170, 233

662 Index

Protecting Groups Third Edition by Philip J. Kocieński

di-tert-butylsilylene 7, 31, 152, 168, 212,223–224, 233, 396

dibutyltin oxide 254, 324dichloracetate esters 32% dichloroacetic acid 479dichloroacetic acid 205, 5872,6-dichlorobenzyl ether 250, 616dichlorobis(triphenylphosphine)palla-

dium(II) 5272,3-dichloro-5,6-dicyano-1,4-benzoquinone

(DDQ) 11, 54–55, 125, 149–150, 152,168, 172, 176, 212, 250, 258, 271, 283,305, 572, 575, 579

2,3-dichloro-5,6-dicyano-1,4-benzoquinonecoated onto molecular sieves 152

2,3-dichloro-5,6-dicyano-1,4-benzoquinonein aqueous acetonitrile 316

2,3-dichloro-5,6-dicyano-1,4-benzoquinoneoxidation 138

dichlorodimethylsilane 289dichloroethylalane 2701,3-dichlorotetrabutyldistannoxane 324N,N0-dicyclohexyl-O-benzylisourea 416dicyclohexylcarbodiimide 102, 109, 409, 438dicyclohexylcarbodiimide–DMAP 432, 435Didemnin 291, 424, 428Didemnones A and B 238dideoxy-l-cladinose 140Diels–Alder reaction 99diethanolamine 568O,O-diethyl trithiodicarbonate 497diethyl acetal 72–73diethylamine 530, 590diethylisopropylsilyl chloride 225diethylisopropylsilyl triflate 225differentially protected chiral ammonia

equivalent 5711,5-dihydro-2,4-benzodioxepine 55Dihydrocodeinone 574dihydrodithiazine 96dihydroerythronolide A 29, 134, 147, 1514,5-dihydro-2-lithio-5-methyl-1,3,5-dithia-

zine 96, 3191,5-dihydro-3-methoxy-2,4-benzodioxe-

pine 55dihydroxylation 3321a,25-dihydroxy-vitamin D 238diimide 490diimide scavenger 490diiodozinc 247di-isopropylsilylene 31, 168

diisobutylalane 120, 145, 153, 199, 216,257, 268, 282, 331, 594

7,20-diisocyanoadociane 64N,N0-di-isopropyl-O-tert-butylisourea 408diisopropyl acetal 74, 75N,N-diisopropyl-bis[2-(methylsulfonyl)-

ethyl] phosphoramidite 481diisopropylethylamine (DIPEA) 192, 324,

452, 495, 511, 533, 553, 561, 570diisopropylsilyl ether 39dimedone 12, 281, 345, 420, 5244,5-dimethoxy-2-nitrobenzyloxycarbo-

nyl 5201,3-dimethoxybenzene 404, 50630,50-dimethoxybenzoin acetate 14,

471–4723,4-dimethoxybenzyl ethers 11, 147, 152,

257–269, 307–308, 572, 577, 5803,4-dimethoxybenzylidene acetal 147, 1523,4-dimethoxybenzyloxymethyl

(DMBM) 306(2,4-dimethoxybenzylthio)-4-methylphenyl

sulfonate 3711,1-dimethoxycyclohexane 1361,1-dimethoxycyclopentane 1364,40-dimethoxydiphenylmethyl, see

bis(4-methoxyphenyl)methyl2,2-dimethoxylpropane 126, 174dimethoxymethane 157, 2933,3-dimethoxypentane 1303,4-dimethoxyphenyl acetals 2682,2-dimethoxypropane 128, 401dimethoxytrityl (DMT) 269–271, 461, 479,

481, 560, 586, 58950-O-dimethoxytritylthymidine 4775,5-dimethyl-1,3-dioxane 59, 176, 332, 524,

541, 568, 606, 611dimethyl acetal 19, 29, 36, 72, 74–76, 79,

84, 86, 99dimethyl N,N-diethylphosphoramidite 460dimethyl disulfide 374dimethyl sulfate 235dimethyl sulfide 62, 231, 304, 460, 513, 582dimethyl sulfoxide 323, 399dimethylacetamide dimethylacetal 620dimethylallyl ester 526dimethylaminomethylene 620N-(3-dimethylaminopropyl)-N0-ethylcarbo-

diimide 1734-dimethylaminopyridine (DMAP) 198,

212, 222, 273, 324, 409, 432, 435, 522, 538

Index 663

Protecting Groups Third Edition by Philip J. Kocieński

dimethylaminosulfur trifluoride 210dimethylaminotrimethylsilane 210dimethylaziridine 109N,N0-dimethylbarbituric acid 387, 420, 525,

594dimethyl-b-cyclodextrin 518dimethyldioxirane 51, 252, 548dimethylformamide di-tert-butyl acetal 409dimethylformamide dimethyl acetal

620–621dimethylisopropylsilyl (DMIPS) 2242,5-dimethylphenacyl esters 162,4-dimethylphenylsulfonyl 5462,2-dimethylpropane-1,3-diol, 58–59N,N0-dimethylpropylene urea 311N,N-dimethylsulfamoyl 623dimethylsulfonium intermediates 3212,7-dimethylxanthen-9-ylidene 1602,20-dinitrodiphenylmethoxycarboyl 5222,4-dinitrophenylsulfenyl 5592,4-dinitrophenylsulfonyl 5511,2-diols 237, 268, 2931,2- and 1,3-diols 14, 229, 261, 2741,3-dioxanes 30, 52, 58, 125, 128, 131, 150,

153, 261, 2931,3-dioxepanes 52–53, 128–129, 296dioxolanation 61–621,3-dioxolanes 26, 29, 32, 52, 56, 58, 61,

73, 94, 97, 120, 125, 128, 131, 139, 145,150, 153, 261, 298, 318

1,3-dioxolanes, cis- and trans-fused 131dioxonium ion 271,2-dipalmitoyl-sn-glycer-3-yl-d-myo-inosi-

tol 1-phosphate 317diphenyl phosphate 482diphenyl sulfoxide/methyltrichlorosilane

384diphenyldiazomethane 416diphenyldichloromethane 160diphenylmethyl (Dpm) 404, 413, 575diphenylmethyl esters 414, 513, 601diphenylmethylamine 573, 601diphenylmethylamines 573diphenylmethylene acetals 155, 158N-diphenylmethylene derivative 600N-diphenylmethyleneamines 600–6012,20-dipyridyl suppressed hydrogenolysis

242, 515di-(2-pyridyl)thiocarbonate 268, 439Discodermolide 95, 152–153, 243Discorhabdin A 369

dissolving metal reduction 92, 138, 158,264, 369, 512, 576, 589

distearoylphosphatidyl-myo-inositol 3,4,5-tris(dihydrogenphosphate) 464

disulfide 380disulfide, disproportionation 380dithianemonosulfoxide 871,3-dithianes 7, 78–79, 94, 321, 544, 5731,3-dithianes ethers 2411,3-dithian-2-yl-methyl 4391,3-dithian-2-yl-phosphonic acid diethyl

ester 1051,2-dithiine ring 375dithioacetalisation 92dithioacetals 77–93, 125, 141, 387–388dithiocarbonate 372dithioerythritol 5591,3-dithiolanes 7, 90dithionite 559dithiothreitol 380–381, 496Ditryptophenaline 312, 574(S)-(+)-2-dodec-3-en-1-olide 101Dolastatins 531Doliculide 211double bonds 242double diastereoselection 162Dowex 58Dowex 50W 121Dowex 50WX2 320Dowex 50WX8 200Dynemicin A 428, 443, 507Dynemicins 36, 211

E1cb mechanism 9Ecteinascidin 369Ecteinascidin-743 376Elaiophyllin 224electric eel cholinesterase 327electrolysis 547, 606electron transfer 13electrophilic aminating agent 511electrophilic thiolation 370a-Eleostearic acid 101Eleutherobin 194, 326Elfavirenz 178b-elimination 17, 57, 59, 74–75, 86, 89,

208, 437, 473, 529, 532–533Ellipticine 622enamide 592enamine 91

664 Index

Protecting Groups Third Edition by Philip J. Kocieński

enediynes 196Enkephalin 530, 601enol ethers 12–13, 275, 279enol silyl ethers 214enolate formation 208enones 39, 55Enopeptin B 441enzymatic hydrolysis 401, 518ephedrine 511Epiantillatoxin 87epichlorohydrin 609epidithiapiperazinedione 387Epothilones 84, 344Epothilones A and B 228, 250epoxidation 31, 66epoxides 31, 66, 136Epoxysorbicillinol 435equatorial alkylation 2546-epi-erythromycin 33, 138–139Erythronolide 320Erythronolide B 90, 274esterases 327esters 9, 11, 16, 242, 395–440ethane-1,2-diol 58, 60, 62ethane-1,2-dithiol 78, 105, 167, 2701,2-ethanedithiol bis(trimethylsilyl) ether

91, 231, 506ethanesulfanyltrimethylsilane 90ethanethiol 78, 122, 140, 231, 247–248,

265, 582ethanolamine in refluxing 2-propanol 3341,2-ethanolamines 564ethanolysis without loss of the labile phe-

nolic TES ether 336ethers 5, 8, 230–285, 4121-ethoxy-1-ethyl ethers 318N-ethoxycarbonyl 503–505N-ethoxycarbonylphthalimide 4932-ethoxyethyl 104, 204, 562ethyl carbamate 595ethyl chloroformate 595ethyl esters 398ethyl trifluoroacetate 500ethyl vinyl ether 318ethyldiisopropylammonium hydrazine-

dithiocarbonate 4751-ethyl-3-[3-dimethylamino)propyl]carbo-

diimide 409, 497ethylenediamine 336, 411, 491, 515, 627ethylidene 141, 147Everinomycin 254

Finkelstein reaction 253FK-506 24, 197, 221fluorene 99-fluorenyl esters 4179-fluorenylmethanol 5349-fluorenylmethoxycarbonyl (Fmoc) 9, 37,

326, 385, 414, 419, 424, 428, 436, 460,488, 528–535, 540, 590

9-fluorenylmethyl (Fm) 9, 376–378,439–440, 474–476, 534

fluoride-induced fragmentation 8fluoroboric acid 237, 256, 3312-fluoroshikimic acid 156fluorosilicic acid 202, 221fluorosiliconate 7fluorotrimethylsilane 7formaldehyde 156formaldehyde scavenger 568, 627formic acid 9, 202, 238, 242, 269, 295, 302,

403, 414, 516, 526formyl anion equivalent 96Fostriecin 214, 260, 466FR-900482 175, 291, 301, 521FR-901228 373FR-900848 68, 206, 397fragmentation reaction 433Fredericamycin 233Friedel–Crafts alkylation 240fructose 573fucosyl-chitobiose 524Fulvine 289, 434Fumagillin 198Fumiquinazoline G 581, 583

Gabriel reaction 489Galanthamine 39, 158Galantin I 602galbonolide B 139Garner’s aldehyde 173–174Gelsemine 562Gilvocarcin 288Ginkolide 101Ginkolide A 289Gliotoxins 387b-d-Glucopyranosyltuberonic acid 337glucosaminic acid 401d-glucose 130, 329glutamic acid 414, 458, 531glutamine 585glycinamide can be added to scavenge the

formaldehyde 303

Index 665

Protecting Groups Third Edition by Philip J. Kocieński

glycine 591, 595, 598, 600glycoconjugate 17glycopeptides 16glycophosphopeptides 16glycosidation 28, 492O-glycosidic links 17glycosphingolipid 226glycosylation 173O-glycosyl-serine 419, 529O-glycosyl-threonine 419glyoxylic acid 84gramine 625guanidine 326, 331guanidine alkaloids 59guanidinylation 614guanine 559, 620guanylation 612l-gulonolactone 155

Hainanolidol 76halogen–metal exchange 99, 598Hamacanthin B 624Hapalosin 289Hemibrevetoxin 141Hemibrevetoxin B 204Hennoxazole 2122,3,4,40,400,5,6-heptafluorotriphenyl-

methyl 41412-HETE 1011,1,1,3,3,3-hexafluoro-2-propanol 271hexahydropyrrolo[3,2-c]quinoline 97hexamethyldisilane 504hexamethyldisilazane 192hexamethyldisiloxane 61hexamethylphosphoramide (HMPA) 233d-threo-2,5-hexodiulose 573HF-7 341Hikizimycin 250Himastatins 547Hirudonine Sulfate 611histidine 622, 628Hitachimycin 535, 579HMG CoA reductase inhibitor 70Hofmann rearrangement 84homocaldopentamine 607homocysteine 380homolysis 13human serum response factor 17Huperzine A 504, 576Hycron 37hydrazine 4, 273, 326, 338, 464, 490, 606

hydrazine in acetic acid–methanol 336hydrazine in methanol 625hydrazinedithiocarbonate 336hydrazinolysis 489hydrazoic acid 559Hydridalactone 101hydride abstraction 157, 322hydride transfer 26hydroboration 332hydrochloric acid 156, 171, 568, 601hydrochloric acid, 1M in dioxane 237, 460,

532, 554, 559, 597, 623hydrochloric acid in THF 559hydrogen 9, 410hydrogen abstraction 16hydrogen bromide 5, 233, 369, 488, 512,

528, 568hydrogen bromide in acetic acid 237, 546hydrogen chloride 204, 219, 287, 366, 378hydrogen chloride in DME at 55 �C 563hydrogen chloride in ether 559hydrogen chloride in methanol 568–569,

597hydrogen chloride in THF 426hydrogen cyanide 559hydrogen donor 15hydrogen fluoride 7, 66, 88, 211, 216, 221,

228, 230, 308, 367, 368, 376, 414, 424,441, 466, 477, 512, 548, 597

hydrogen fluoride and anisole 555, 617hydrogen fluoride in acetonitrile 201, 220,

428hydrogen fluoride�pyridine 197, 205, 216,

220, 224, 229, 464, 597hydrogen fluoride� triethylamine 216–217,

221hydrogen iodide 559hydrogen peroxide 31, 277, 344, 488hydrogen sulfide 372–373, 559hydrogenation 611hydrogenolysis 6, 56, 97, 137–138, 158,

173, 178, 238, 241, 271, 339, 341, 413,417, 462, 464, 481–482, 515, 517, 520,530, 540, 563, 573–574, 584, 586, 588,612, 621

hydrogenolysis of BOM ethers in the pre-sence of alkenes 302

hydrogenolysis of p-nitrobenzyl (PNB) 413hydrolysis 51, 71, 75, 86, 88, 91, 95, 97,

99–101, 106–107, 121, 158, 175hydrolysis, basic 498

666 Index

Protecting Groups Third Edition by Philip J. Kocieński

hydroperoxide 318hydroxamic acids 244, 312b-hydroxy ketones 54, 94, 106, 170, 5231-hydroxybenzotriazole 559hydroxylamines 535hydroxyl-directed reduction 701,1,1-2-hydroxymethyl-2-methyl-propane-

1,3-diol 102, 384, 386Hygromycin A 61hypophosphorous acid, 50% aqueous 553Hypusine 379

imidate ester 109imidazoles 192, 198, 212, 222, 229, 621,

625–626, 629imide 4, 492iminium salt 97iminodithiocarbonates 599Inandenin-12-one 538indoles 510, 621–622, 624–627indoline N-benzyl groups 574Indolizomycin 535inositol-1,4,5-triphosphate 272, 467Integerrimine 206, 322, 427intramolecular hydride transfer 145intramolecular hydrosilylation 170intramolecular transesterification 3–4, 326iodine 7, 24, 64, 81, 105, 122, 141, 205,

269, 277, 375–376, 382, 384, 477, 502,504

iodide, as nucleophile 12iodine, aqueous 465iodinolysis 3729-iodo-9-borabicyclo[3.3.1]nonane 231p-iodobenzyl ether 212-iodoethyl ester 432iodomethane 87, 107, 233, 235–236, 321,

599iodomethane in aqueous acetone 427N-iodosuccinimide (NIS) 29, 165iodosylbenzene 75iodotrimethylsilane 5, 54, 192, 231, 233,

238, 247, 264, 283, 289, 296, 319, 413,458, 504, 509, 514, 563, 573

ion exchange resins 121, 126, 316–317, 320iron(III) chloride 54, 123, 126, 238, 247,

258, 270, 298iron(III) chloride adsorbed on silica 317iron(III) chloride hexahydrate 54, 124isobutene 239, 407isocyanate 536

Isolaurallene 250isomerisation 13, 275–276, 278isopropenyl ether 126isopropenyl methyl ether 127isopropoxytrimethylsilane 63isopropyl aryl ethers 235isopropyl ethers 5isopropyl phosphonate 166isopropylidene 6, 72, 91, 127, 130,

140–141, 158, 160, 168, 206, 269, 478,509, 517, 620

isopropylidene acetals 138, 141, 145, 150,258, 265, 269, 288

Jesterone 66Jones oxidation 95, 488

(–)-K252a 580K-13 498, 514KDO 402ketene dithioacetal 105g-keto acid 97ketone 261kinetic control 61, 128kinetic resolution 328Koenigs–Knorr glycosidation 27, 489

L-733,725 629Lactacystin 176d-lactal 284b-lactams 404, 490, 566, 576, 580–581,

592, 596, 598lactol 95lactone 95, 105lactose 226Lankacidin 100, 123Lankacidin C 202Lanosterol 91lanthanum(III) chloride 77Lapidilectine 569laser flash photolysis 15Latrunculin 308, 579Latrunculin B 577Laulimalide 288Laurencin 250, 331lead tetraacetate 488lead(II) nitrate 590lead(IV) 83Leinamycin 261, 438Lepicidin 534Lepicidin A 395

Index 667

Protecting Groups Third Edition by Philip J. Kocieński

Leucascandrolide A 397Leuchs anhydrides 585tert-leucinol 96Leukotriene B4 400levulinic acid 96levulinoyl 464, 4752-[2-(levulinoyloxy)ethyl]benzoyl (PACLev)

esters 474linker 37lipase M 17lipases 327Lipid A 465Lipogrammistatin A 605lipopeptides 16Lipstatin 74lithiation, directed 622–6236-lithio-3,4-dihydro-2H-pyran 161lithium 11, 51, 141, 158, 245, 303, 372, 546lithium aluminium hydride 107, 503, 546,

559lithium aluminium hydride–trichloroalane

142, 145lithium benzenethiolate 458lithium borohydride 498, 568lithium bromide 157lithium chloride 233lithium cyanide 464lithium di-tert-butylbiphenylide 303lithium di-tert-butylimidodicarbonate 511lithium diisopropylamide 30, 137, 176, 568lithium dimethylcuprate 33lithium diphenylphosphide 234lithium ethanethiolate 233lithium hexamethyldisilazide 100, 162, 465lithium hydroperoxide 395, 578lithium hydroxide 212, 331, 395, 499, 539lithium in ethylamine 576lithium in liquid ammonia 543lithium iodide in hot collidine 413lithium iodide in refluxing collidine 399lithium iodide in refluxing pyridine 399lithium N-methylanilide 25lithium [a-methylbenzyl]allylamide 592lithium (a-methylbenzyl)(3,4-dimethoxy-

benzyl)amide 571lithium naphthalenide 246lithium tetrafluoroborate 57, 74, 291, 309lithium p-thiocresolate 233lithium tri-sec-butylborohydride 109lithium triethylborohydride 342lithium–halogen exchange 107

Loganin 77Lonomycin A 2272,6-lutidine 82, 84, 170, 213, 222, 321, 342,

406Luzopeptins A–C 530, 555Lycoricidine 579lysine 37, 587, 606Lysobisphosphatidic Acid 478Lythrancepine 248Lyxose 136

Macbecin 260Macbecin I 499Macrocarpal C 233macrocyclisation 100macrolactonisation 134, 433Macrosphelide A 295Madumycin II 139, 289, 399Magellanane alkaloids 332Magellanine 573magnesium bromide 88, 316, 318, 428magnesium bromide etherate 265, 317magnesium bromide in ether containing

nitromethane 309magnesium chloride 296magnesium iodide 232, 296magnesium metal in methanol 546, 623magnesium methoxide 326, 331magnesium sulfate 58, 90b-manno glycosides 262Manumycin 527Manzamine 545Manzamine A 557Martinellines 97Medetomidine 623Meisenheimer complex 549mercaptoacetic acid 5502-mercaptobenzoic acid 5932-mercaptobenzothiazole and DIPEA in

N-methylpyrrolidinone 458mercaptoethanol 367, 382, 471, 496, 550,

559, 605mercaptoethanol and DBU 6052-mercaptoethylamine 3363-mercaptopropionitrile 3752-mercaptopyridine 496mercury(I) 93mercury(II) 7, 93–94, 96, 104, 106, 275,

367, 372, 382mercury(II) acetate 300mercury(II) chloride 79, 276, 320, 616

668 Index

Protecting Groups Third Edition by Philip J. Kocieński

mercury(II) oxide 79–80, 276mercury(II) perchlorate 81, 322mercury(II) trifluoroacetate 369, 371mesitylenesulfonamide 548mesitylmethylene acetals 137–139meso trick 400metal hydride 624metallated cyanohydrins 100metallation 35, 93, 107, 625metallation, directed 598metallation, heteroatom-assisted 35methanesulfonic acid 226, 233, 249, 380,

506, 512methanol 191methanolysis using potassium carbonate

344methionine 233, 525p-methoxybenzaldehyde dimethylacetal

176, 258, 387p-methoxybenzenesulfonamide 545p-methoxybenzoate 149, 330p-methoxybenzyl (PMB) 88, 257–269,

368–371, 465–467, 577–585p-methoxybenzyl ethers 11, 22, 24, 26, 55,

123, 130, 133, 144–145, 153, 175–176,242–243, 260, 265–268, 290, 305, 307,368, 404, 410–411, 413, 416, 465, 517,536, 544, 549, 577, 584

p-methoxybenzyl mercaptan 3694-methoxybenzylamine 267p-methoxybenzylidene acetals 134,

137–138, 149–150, 387, 5664-methoxybenzyloxycarbonyl 517N-methoxycarbonyl 5052-(2-methoxyethoxy)ethyl (MEE) esters 172-methoxyethoxymethyl chloride 3002-methoxyethoxymethyl (MEM) 6, 34,

242, 295–301, 426–430a-methoxyhydroperoxide 74methoxymethyl (MOM) 6, 16, 32, 216,

242, 258, 294, 309, 316, 557, 562, 565methoxymethyl ester 426–430methoxymethyl ethers 156–157, 285–295,

508, 5792-(p-methoxyphenyl)-1,3-oxazolidine 176,

212, 268, 274p-methoxyphenylethylene acetal 552-methoxypropene 126–128, 130, 3184-methoxytetrahydropyran-4-yl ethers 3174-methoxy-2,3,6-trimethylphenylsulfonyl

(Mtr) 617–618

methoxytrimethylsilane 77a-methoxyvinyllithium 298methyl benzyl N,N-diisopropylphosphora-

midite 463methyl carbonate 399methyl dihydroquinate 166methyl dithiocarbamate 599methyl esters 395–403methyl ethers 5, 27, 230–237, 573methyl b-hydroxypropionate 438methyl a-d-mannopyranoside 164–165methyl methanethiosulfonate 92methyl orthoformate 55, 165methyl phosphates 457–460, 464methyl trifluoromethanesulfonate 87,

235–236methylamidine group 620(+)-O-Methylancistrocline 107N-methylaniline 38, 419N-methylation 107, 321p-methylbenzyl 368p-methylbenzylsulfonyl group 548, 5542-methyl-2-butene 2692-(methyldiphenylsilyl)ethyl (DPSME)

group 478methylene acetals 289methylhydrazine 4906-methyl-1-indanone 16, 31, 60, 102, 192,

240, 401, 458, 501, 552, 583methylmagnesium iodide 234N-methylmorpholine 277, 332methylnitropiperonyloxycarbonyl 522methylrhenium trioxide 3442-(methylsulfonyl)ethyl esters 4372-(methylsulfonyl)ethyl phosphates

480–481methylsulfonylmethyl esters 427(methylthio)dimethylsulfonium tetrafluo-

borate 374methylthiomethyl (MTM) 7methylthiomethyl esters 427methylthiomethyl ethers 34, 94, 241Methynolide 309Micacocidin 369migration 3, 68, 206, 214–216, 247, 324, 338migration of double bond 63Milbemycin D 309Milbemycins 54, 274Mirabazole C 369Mitsunobu reaction 215, 257, 433,

549–550, 557–558, 603

Index 669

Protecting Groups Third Edition by Philip J. Kocieński

mixed carboxylic–carbonic anhydrides 423Miyakolide 411Moenomycin 482molecular oxygen 579molecular sieves 58, 60, 126, 128–129, 208Monensin 148, 275, 310mono- and di-allylamines 593Monocrotalic Acid 215Monocrotaline 157monomethoxytrityl (MMT) 270, 586–587(+)-Monomorine 97Montmorillonite clay 126, 316MoOPh 579morphine 544morpholine 9, 12, 281, 419, 529Motuporin 260, 424Muamvatin 170Mucin-type glycopeptides 37Mucor miehei lipase 330, 518Mucor javanicus 17Muricatetrocin 167Muscaflavines 532Muscone 100Mycalamide B 157, 293, 536Mycalamides 563Mycinolide 420Mycobactin S 312Mycotrienol 72, 220Myxovirescin A1 217

N1999-A2 196, 336naphthyl ether 6122-naphthylmethyl 244, 251–252, 412, 5202-naphthylmethylene (NAP) acetals 142Naproxen 68Narciclasin 579Nargenicin 108Nazarov cyclisation 226neighbouring group participation 489, 492,

501Neocarzinostatin 73Nephilatoxin-9 606Nephritogenoside 345Nephrosteranic Acid 106nickel(0)-catalysed hydroalumination–

elimination 282nickel(II) chloride (dppb) and lithium

triethylborohydride 282Nicotianamine 343Nisamycin 72nitrile 99, 103

nitro group cleaved by transfer hydrogeno-lysis 612

nitro groups 242, 341, 369, 411, 559Nw0-nitroarginines 6114-nitrobenzaldoxime 4702-nitrobenzenesulfenyl 469, 560–5612-nitrobenzenesulfenyl chloride 3672-nitrobenzenesulfonamides 550, 6052-nitrobenzenesulfonyl chloride 5502-nitrobenzyl 14, 252, 341, 413, 582–5832-nitrobenzylidene acetals 14p-nitrobenzyloxycarbonyl (PNZ) 340–341,

516–517p-nitrocinnamyloxycarbonyl (Noc) 528nitroimidazole–polyamine conjugates 6082-(4-nitrophenyl)ethyl (NPE) 481, 522o-nitrophenylacetamide 501p-nitrophenyldiazomethane 4162-nitrophenylsulfenyl chloride 382,

559–5612- and 4-nitrophenylsulfonyl (Ns)

548–552, 604–6052-nitrosobenzaldehyde 14nitroveratryl 6192-nitroveratryloxycarbonyl 520Nocardicinic acid 490NodRf-III 208, 492NodRm-IV factors 200Nogalamycin 281, 283, 2885-norbornene-2,3-dicarboximido chlorofor-

mate 523Norrish type II process 14nucleopeptides 17nucleophilic cleavage 464nucleophilic cleavage of the N-sulfonylazir-

idine 557nucleophilic demethylation 36nucleophilic dithioacetalisation 92nucleophilic scavenger 420, 467nucleophilic substitution 106, 398nucleophilic thioacetalisation 91Nummularine F 514

Obafluorin 559Obtusenyne 257OF 4949 III 432Okadaic Acid 246Oleandolide 141, 152, 221olefins 411Oligomycin C 30Olivomycin A 281, 303, 336

670 Index

Protecting Groups Third Edition by Philip J. Kocieński

Omapatrilat 380orange peel acetyl esterase 518organocuprates 35ornithine 610, 612, 614orthoester formation 28orthoesters 100–107, 109, 294, 332osmium tetroxide 13, 126, 277, 332, 488,

592Ovatolide 627oxalic acid 731,3-oxathianes 931,3-oxazinanes 566oxazole 532oxazolidine 175oxazolidinone 563oxazoline 177oxazolinium salt 109oxetane 102oxidation 65, 81, 375oxidation of allylic amine function to give

ketone 260oxidative cleavage 7, 148–149, 251, 580oxidative coupling 39oxidative cyclisation 152–153oxidative deprotection 382oxidative dethioacetalisation 84oxidative hydrolysis 81, 86, 260, 277oxidative ring contraction 75oxindole 562oxiranes 54oxonium ion 5, 11, 29, 81(R)-4-oxo-5-phosphononorvaline 458oxytocin 368ozone 13, 51, 137, 168, 488ozonolysed to very labile formate ester

279ozonolytic cleavage 147

Paenoflorin 194palladium 9, 11, 38, 241, 276palladium-catalysed extrusion of CO2 from

allyloxycarbonyl 284, 418palladium-catalysed hydrogenolysis 568palladium hydroxide 241, 621palladium on carbon 410, 594palladium supported on barium sulfate 244palladium(0) catalysed allylation of an

amine 595palladium(0) catalysis 467, 594palladium(0) catalysts 12, 281, 345–347,

524, 593

palladium(II) 148palladium(II) acetate 66, 420, 526palladium(II) acetate and triethylamine in

the presence of triethylsilane 412palladium(II) chloride(MeCN)2 54palladium(II) chloride, Ph3P and ammo-

nium formate in dioxane 4181-O-palmitoyl-3-O-phosphosphoryl-sn-gly-

cerol 461Pancratistatin 545Paniculide 287papain 17Papulacandin 210Papulacandin D 169, 396Paraherquamide A 508Park nucleotide 437, 499Pateamine 541Pearlman’s catalyst 302, 570Pederin 433penem allyl ester 421penicillin G acylase 19, 385, 518pent-4-enoic anhydride 502N-pent-4-enoyl 502pentachlorophenylsulfenyl 559pentadienyl anion 11N-pentafluorophenyl-N-allyloxycarbonyla-

minomethyl sulfonium tetrafluoroborate387

pentafluorophenyl (Pfp) esters 496pentafluorophenyl diphenylphosphinate

6182,2,5,7,8-pentamethylchroman-6-ylsulfonyl

6172,2,4,6,7-pentamethyldihydrobenzofuran-5-

ylsulfonyl 6171,2,2,6,6-pentamethylpiperidine 324(S,S)-(+)-pentane-2,4-diol 662,4-pentanedione 4823-pentanone 130n-pentenyl glycosides 284-pentenylmagnesium bromide 97Peptide T 326perchloric acid 129, 408Perhydrohistrionicotoxin 61periodic acid 86Periplanone B 65, 100PGD2 89PGE1 derivatives 421phase transfer catalysis 236, 560, 600phenacyl 14phenacyl bromide 425

Index 671

Protecting Groups Third Edition by Philip J. Kocieński

phenacyl derivatives 15(S)-phenethylamine 584phenol 379, 506phenolate anion 11phenolic benzyl ethers 411, 530phenolic tert-butyl carbonate 342phenolic chloroacetate 336phenols 210, 240, 242phenols as their Boc derivatives 342phenoxyacetates 333phenoxythiocarbonyl chloride 372S-phenylacetamidomethyl 3844-(phenylacetoxy)benzyloxycarbonyl 19,

518l-phenylalanine, N-Boc 16, 510, 5522-phenylbenzofuran 14p-phenylbenzyl ethers 244, 247phenyldiazomethane 256phenyldimethylsilane 229phenylenediamine 3362-phenylethoxycarbonyl group 5309-phenylfluoren-9-yl (PhFl) 414–415,

587–591(R)-(-)-phenylglycinol 97phenylglycine 552phenylsilane 387, 5264-(phenylsulfonyl)methyl-1,3-dioxolane 57,

437, 529–530, 532, 622–6232-(phenylthio)ethyl acetal 19, 549phenylthiolate as nucleophile 12phenylthiotrimethylsilane 95, 2472-phenyl-2-(trimethylsilyl)ethyl

(PTSME) 436, 5389-(9-phenyl)xanthenyl ethers 272Philanthotoxin-433 606Phorboxazole 258Phorboxazole A 218phosgene 522–523, 538phosphate methyl esters 457–460, 464phosphines 384N-phosphinoyl 608phosphodiesters 453phosphoramidite approach 453phosphoranylideneamine 21phosphoric acid 239phosphorus oxychloride 319phosphorus pentoxide 157, 293phosphotyrosines 459photochemical bromination 251photocleavage 13, 520photocyclisation 13

photodeprotection 252, 425, 521, 583photolysis 583, 619photooxygenation 13photorelease 472phthalic anhydride 493phthalide orthoester 21phthalimides 4, 563, 606Phyllanthoside 279Phyllanthostatin 196Phyllanthostatin I 336Picrotoxane 305Picrotoxinin 23pig liver esterase 327pig pancreatic lipase 327, 329Pillaromycinone 168Pinner reaction 103piperidine 9, 376, 439, 488, 529, 625piperidinethiocarboxamide 501pivalaldehyde 176pivalate esters 3, 28, 227pivaloyl chloride 324pivaloyloxymethyl (Pom) esters 407, 620Plakorin 318plasmogens 264platelet-activating factor (PAF) 280platinum 241, 413Pleuromutilin 287polyamines 602Polycavernoside A 250polystyrene resins 37porcine pancreatic lipase 401potassium tert-butoxide 13, 240, 408, 533, 563potassium tert-butoxide in DMSO 275potassium carbonate 3–4, 234, 326, 331,

439, 550potassium carbonate in aqueous methanol

498potassium carbonate in methanol 190potassium carbonate in methanol or

HOAc–H2O–THF 441potassium carbonate in refluxing aqueous

methanol 622potassium carboxylate 467potassium cyanide 326, 337potassium fluoride dihydrate 536potassium fluoride in DMSO 345potassium fluoride on alumina 211potassium fluoride trihydrate 208potassium fluoride-impregnated alumina

284potassium hexamethyldisilazide 153

672 Index

Protecting Groups Third Edition by Philip J. Kocieński

potassium hydride 25310% potassium hydroxide 218, 526, 595potassium hydroxide 92, 503potassium iodide 518potassium peroxydisulfate 580potassium phenoxide 552potassium thioacetate 387potassium trimethylsilanolate 396proline 552, 567propane-1,3-diol 58propane-1,3-dithiol 78, 105, 177, 496propane-1,2,3-triols 131, 1531,3-propanolamines 564propargylic epoxides 123propargylsilane 70propenyl acetate 327propenyl ether 465(Z)-1-propenyl ether 275–276(R,R)-4-propyl-9-hydroxynaphthoxazine

2331,3-propylene bis(p-toluenethiolsulfonate)

91propylidene 216Prostaglandin D 201Prostaglandin D2 101Prostaglandin E1 101protease 406protection of a ketone in the presence of

an aldehyde 62Protolichesterenic Acid 106(1S,2S)-(+)-pseudoephedrine 98pseudomonas cepacia lipase 327Pseudomonic acid 148(R)-(+)-Pulegone 94Pumiliotoxin 74Pummerer rearrangement 87Pyrenolide D 75Pyrenophorol 318pyridine 171, 192, 243pyridine, aqueous 336, 469pyridine-2-aldoxime 4702,6-pyridinedicarboxylic acid N-oxide 306pyridine-2-sulfonamides 606pyridine-2-sulfonyl 606pyridinium hydrobromide perbromide 68pyridinium p-toluenesulfonate 6, 52, 57,

58, 72, 77, 86, 102, 121, 126–127, 150,153, 168, 191, 197, 200, 208, 216, 269,296, 314, 316, 318–319, 441

pyridinium p-toluenesulfonate in refluxingethanol 308

pyrophosphoryl myo-inositol pentapho-sphates 463

pyrroles 621, 623, 625–626pyrrolidine 491, 552, 573o-pyrrolidinocarbonylbenzamide 491

Quinocarin 123quinone 376

Radiosumin 397Raney nickel 11, 241, 243, 303, 411, 584Rapamycin 84, 195, 346, 399rearrangement 12reduction 490reduction of the azide 612reduction of the azido group with dithio-

threitol 612reductive alkylation 584reductive S-alkylation 371reductive amination 39, 97, 573–574, 586reductive cleavage 97, 120, 137, 141–142,

145, 147, 153, 175, 227, 281, 294, 346,367, 372, 431–432, 482, 491–492, 516,543, 546

reductive cleavage to the correspondingmethyl ethers with borane 306

reductive elimination 418, 481, 540reductive fragmentation 24relay deprotection 275, 322, 332, 341, 382,

439, 501resolving agent 162Retigeranic acid 101retroaldolisation 61, 208Rhizobitoxine 512Rhizopus javanicus lipase 330Rhizoxin 105, 260Rhizoxin D 309rhodium 241rhodium(I)-catalysed isomerisation 13, 528Ribasine 590Rifamycin 148ring closing metathesis 31Rishirilide B 434Ro32-3555 410Routiennocin 627(–)-Roxaticin 126, 158Rutamycin B 30ruthenium catalysis 279, 418

SE20 reaction 30SN2 reaction 373, 402

Index 673

Protecting Groups Third Edition by Philip J. Kocieński

SN20 reaction 65SNAr reaction 107–108Salicylihalamide 31Salinomycin 105, 170, 197samarium(II) iodide 344, 432, 606samarium(III) chloride 54(–)-Sandramycin 556Sanglifehrin 342Sanglifehrin A 23Sanjonine G 570Sarain A 577Sarcodictyin 197Sarcophytol-A 100Saxitoxin 573scandium triflate 77, 324scavengers 250, 265, 367–368, 371, 379,

404, 414–415, 460, 506(–)-Schizandrin 108Scytophycin C 170selenium 431selenium dioxide 226, 277selenoxide elimination 64self-regeneration of stereocentres 567serine 17, 102, 173, 238–239, 326, 406,

461, 556, 601serine phosphate 518Sesbanimide 147, 156Sharpless asymmetric dihydroxylation 55Shikimic Acid 157, 274Silphenene 226silver(I) 7, 104, 372, 382silver(I) nitrate 81–82, 84, 219, 321–322,

561silver(I) oxide 81, 236, 253silver(I) perchlorate 81, 103, 502silver(I) tetrafluoroborate 375silver(I) triflate 268, 294silver(I)-assisted solvolysis 68silver(I)-assisted hydrolysis 81silver(I)-assisted oxidative hydrolysis 92silver(I)-assisted silylation 215silver(I)-mediated cleavage 93silyl ester 5901,2-silyl migration 122, 226silylamines 595N-silylpyridinium triflates 194Simmons-Smith reaction 67–68Sinensal 73single electron transfer 11sodium 11, 51, 141, 245, 264, 303, 367sodium amalgam 543, 564, 623

sodium anthracenide 544, 546sodium bis(2-methoxyethoxy)aluminium

hydride 96, 174, 503, 546sodium borohydride 178, 281–282, 384,

432, 488, 491–492, 496, 498, 526–527,559, 584

sodium bromate 251sodium carbonate 595sodium carbonate in methanol 333sodium chloride 232sodium chloride in refluxing wet DMF 399sodium cyanoborohydride 142, 144–145,

573, 584sodium dithionite 553sodium ethanethiolate 36, 233sodium hexamethyldisilazide 536sodium hydride 166, 253, 532, 568sodium hydrogencarbonate in aqueous

DMF 425sodium hydrogencarbonate in methanol

191, 337sodium hydrogensulfate 101–102sodium hydrogensulfite 557sodium hydrogensulfite in refluxing aqu-

eous ethanol 553sodium hydrosulfide 518sodium hydrosulfite 414sodium hydroxide 100, 171, 218sodium in liquid ammonia 271, 546, 559,

574, 576sodium iodide 54, 231, 595sodium iodide in acetone 458sodium methoxide in methanol 625sodium naphthalenide 367sodium in liquid ammonia 543sodium periodate 592sodium salt of 2-ethylhexanoate 418sodium sulfide 414sodium telluride 431sodium 2-thiophenetellurolate 541sodium p-toluenesulfinate 422sodium triphenylmethylthiolate 372sodium/anthracene 498solvolysis 13, 16, 68solvomercuration 80Somatostatin 499Somatostatin inhibitor 37d-sorbitol 156(–)-Sparteine 35(–)-Spergualin 612spermidine 602

674 Index

Protecting Groups Third Edition by Philip J. Kocieński

Spermine 602, 611d-erythro-sphingomyelin 457d-erythro-sphingosine 174, 473, 576sphingosines 601spider neurotoxins 602spider toxin HO-416b 605spiroacetal 88spirocyclic O,S,S-orthoesters 105spiroindolone 563Spirotryphostin 399(–)-Spirotryprostatin B 563Sporidesmins 387STABASE 597–599stannoxane 251stannylene 254, 274, 284stannylene activation 293Staurosporine 258, 563, 627d-erythro-2-N-stearoylsphingosine 457Steglich esterification 432Stigmastellin A 263Streptazolin 248Streptothricin 589Strychnine 65, 222, 499, 545, 568subtilisin 328sulfilimine 83sulfites 559sulfone 20sulfone, a;b-unsaturated 34, 60, 62–63, 65sulfoxonium ylide 376sulfur monochloride 367sulfur tetrafluoride 210sulfuric acid 126, 129, 136, 239, 506Surugatoxin 437Suspensolide 106Swern reagent 376Swinholide 170, 397

TA-949 207, 420Tabersonine 552(Z,E)-Taiwanin 426TAN-1057A 617TAN-1251C 53tartaric acid 68tartrate acetals 68TAS-F 218, 224, 537Tautomycin 79, 152, 224, 226, 306, 405Taxol 26, 90, 99, 148, 169–170, 176, 210,

318, 334, 551, 566Taxusin 298Teichoplanin 214, 231, 499, 537, 540Teleocidin 623

temporary protection 99, 590, 597, 614,625

Terramycin 287tertiary alcohols 54, 253tertiary allylic alcohol 55, 72tertiary amines 1712,3,5,6-tetra-O-acetyl-d-glucofuranose 478tetrabenzyl diphosphate 465tetra-tert-butoxydisiloxane-1,3-diyl 171tetrabutylammonium bromide 289tetrabutylammonium chloride 536tetrabutylammonium chloride and potas-

sium fluoride dihydrate in DMF 433tetrabutylammonium fluoride (TBAF) 7,

99, 169, 171, 173, 193, 196, 207, 215,217–218, 220, 311, 314, 374–375, 414,433, 437, 439, 458, 477, 529, 534–535,554, 556–557, 563, 568, 597, 627

tetrabutylammonium fluoride bufferedwith acetic acid 224, 479

tetrabutylammonium fluoride in THF-buffered with ammonium chloride 198

tetrabutylammonium fluoride trihydrate326

tetrabutylammonium hydroxide 332tetrabutylammonium iodide 95, 253, 304,

314tetrabutylammonium salt 7tetrachlorophthalic anhydride 491tetraethylammonium fluoride 3101,1,3,3-tetraethyl-1,3-disilaisoindolines 599tetrafluoroboric acid 367N-[2,3,5,6-tetrafluoro-4-(N0-piperidino)-

phenyl]-N-allyloxycarbonylamino-methyl 386

tetrafluorosilane 204tetrahydrofuran, aqueous 225tetrahydrofurans, synthesis 149tetrahydrofuran-2-yl 629–6301,2,3,4-tetrahydro-1-naphthyl esters 413tetrahydro-1,3-oxazine 566Tetrahydropseudodistomin 568tetrahydropyran-2-yl 6, 33, 37, 57, 104,

133, 202, 204, 216, 242, 258, 288, 335,379, 428, 441, 508

1,1,3,3-tetraisopropyldisiloxane-1,3-diyl 7,284

tetrakis(triphenylphosphine)palladium(0)345, 347, 526

2,2,3,3-tetramethoxybutane 1651,1,2,2-tetramethoxycyclohexane 164

Index 675

Protecting Groups Third Edition by Philip J. Kocieński

tetramethylammonium acetate in HMPA399

N,N,N0,N0-tetramethyl-1,2-ethylenediamine(TMEDA) 169, 347, 597–598

1,1,3,3-tetramethylguanidine 222, 272, 469tetramethylguanidinium azide 21Tetraponerines 5501H-tetrazole 458, 621Tetrazomine 592Tetronasin 124thallium(III) 83, 367thallium(III) trifluoroacetate 382Thermitase 406thermodynamic control 61, 128thermolysis 625thermopentamine 606thexyldimethylsilyl chloride 227Thiangazole 378Thiarubrine C 375Thielocin A1 431Thienamycin 107, 148, 413, 596thioacetalisation 90thioacetamide 559thioacetates 21thioanisole 247, 250, 295, 367, 404, 414,

460, 506, 513, 580, 616, 618Thiocoraline 382p-thiocresol 368, 559thioethers 241, 366–377thioglycolic acid 367, 559thioglycosidation 370thiol esters 3(S)-thiolactic acid 373thiolane 5thiolate anions 400thiols 39, 89, 365–392, 548thionium ion 26thiono–thiolo rearrangement 479thionyl chloride 109, 488, 558thiophenols 289, 496, 506, 559thiosulfate 559thiourea 336, 501, 559Thorpe-Ingold effect 58threonine 17, 37, 174, 238–239Thromboxane A2 397thymidine 322thymine 559tin(II) chloride 127, 237tin(II) chloride dihydrate 265tin(II) triflate 267tin(IV) chloride 32, 136, 170, 247, 265, 296

Tirandamycic Acid 300Tirandamycin 202Tirandamycin B 580titanacyclopropane 282titanium(IV) chloride 70, 75, 91, 97, 142,

168, 238, 298, 511titanium(IV) isopropoxide 282p-toluenesulfinic acid 422p-toluenesulfonamides 544, 546, 617, 624p-toluenesulfonate esters 57, 86p-toluenesulfonic acid monohydrate

(PTSA) 53, 58, 62, 77, 122, 126,128–130, 150, 157, 171, 177, 216, 220,224–225, 239, 319, 326, 403, 538, 553,557, 559, 567

p-toluenesulfonyl (tosyl) 258, 369, 498,533

Tolyporphyrin A 248torsional deactivation 1642-tosylethoxycarbonyl 5322-tosylethyl esters 437transacetalisation 52–53, 55, 60, 84, 140,

177transacylation 21transesterification 327, 3321,5-transfer of hydrogen 14transfer catalytic conditions 530transfer catalytic hydrogenation 9, 242,

516transprotection 79, 84, 86, 90–91, 491,

505, 550, 555, 595, 6062-(trialkylsilyl)ethyl phosphorothioates 479trialkylsulfonium salts 871,2,4-triazole 62120,30,50-tri-O-benzoyladenosine 478tribromoalane 231, 582tribromoborane 5, 27, 231, 248tributylphosphine 369, 374, 384, 469tributylstannane 281, 370, 386, 467,

526–527, 559–560tributylstannyl esters 407tributylstannyl ethers 255tributylstannyl thiolate 370trichloracetate esters 3trichloroacetic acid 74trichloroacetimidate 240trichloroacetonitrile 240, 284, 408trichloroalane 91, 126, 143, 230–232, 235,

414trichloroalane–N,N-dimethylaniline 4282,4,6-trichlorobenzoyl chloride 409, 438

676 Index

Protecting Groups Third Edition by Philip J. Kocieński

trichloroborane 5, 230, 235, 247, 289, 304,313, 388, 505, 514

trichloroborane�dimethylsulfide 248, 2652,2,2-trichloro-tert-butoxycarbonyl (Tcboc)

6072,2,2-trichloro-1,1-dimethylethyl

(TCB) 481–4822,2,2-trichloroethanol 4322,2,2-trichloroethoxycarbonyl (Troc) 9,

175, 343–344, 428, 540–542, 575, 6072,2,2-trichloroethoxymethyl 5642,2,2-trichloroethoxymethyl ethers 9trichloroethyl acetate 3272,2,2-trichloroethyl carbonates 9, 326, 343,

542, 5752,2,2-trichloroethyl esters 8, 382Tricolorin A 149Trienomycin A 564triethyl orthoformate 135triethylalane 282triethylamine 192, 233, 480triethylamine in DMF or dioxane 458triethylamine trihydrofluoride 197, 207,

443triethyl-oxonium tetrafluoroborate 87triethylsilane 32, 81, 97, 144, 147, 229, 265,

371–372, 516triethylsilyl (TES) 7, 59, 191, 195–199,

440–444, 516triethylsilyl ethers 55, 195–199, 466triethylsilyl triflate 29, 126, 192, 198, 406triflic acid, see trifluoromethane-

sulfonic acidtrifluoroacetamides 4, 499, 540, 611trifluoroacetate esters 3, 157trifluoroacetic acid 5, 37, 109, 121–122,

139, 144–145, 158, 162, 164, 166, 171,176, 191, 196, 203, 216, 237–238, 250,265, 287, 295, 309, 312, 326, 367–369,371–372, 379, 382, 403, 410, 413–414,424, 435, 460, 506, 511, 513, 528, 529,538, 554, 561, 566, 579–580, 582, 589,614, 616–618, 625

trifluoroacetic acid in a phenol matrix 404,410

trifluoroacetic acid in dichloromethane 517trifluoroacetic anhydride 156, 375, 500,

568trifluoroacetonitrile 267trifluoroacetoxymethyl acetal 156N-trifluoroacetylation 500

N-(trifluoroacetyl)succinimide 500, 606trifluoroborane 5, 237, 239–240, 247, 265,

304trifluoroborane etherate 80, 89–91, 102,

135, 143, 166–168, 204, 226, 231, 240,267, 270, 289, 373, 423, 513, 566

trifluoroborane etherate in acetic acid 508trifluoroborane in dichloromethane–

methanol 2712,2,2-trifluoro-1,1-diphenylethanesulfen-

amides 559trifluoroethanol 122, 177N-trifluoromethanesulfonamides 603trifluoromethanesulfonic acid 122, 144,

165, 177, 213, 225, 240, 256, 384, 460,512

trifluoromethanesulfonic acid in 2,2,2-tri-fluoroethanol 240

trifluoromethanesulfonic anhydride 754-trifluoromethylbenzyl carbamate 5202,4,6-triisopropylbenzenesulfonyl chloride

482triisopropylsilane 415triisopropylsilyl (TIPS) 7, 191, 197, 202,

218–223, 239, 270, 395, 440–444,625–626

triisopropylsilyl chloride 222triisopropylsilyl esters 443triisopropylsilyl ethers 36, 55tri-isopropylsilyl ethers 169triisopropylsilyl triflate 2222,4,6-trimethoxybenzyl 368, 3714,40,400-trimethoxytrityl 586, 589trimethyl orthobenzoate 177trimethyl orthoformate 77, 294trimethylacetamidomethyl (Tacm) 385trimethylaluminium 69, 105trimethyloxonium tetrafluoroborate 87,

236trimethylsilyl cyanide 99–100, 194trimethylsilyl esters 401, 422, 590trimethylsilyl ethers 22, 34, 100, 166, 443trimethylsilyl triflate 61, 63, 77, 157, 192,

194, 247, 292, 341–342, 367, 405, 460,507

2-(trimethylsilyl)ethoxycarbonyl (Teoc)344–345, 534–540, 575

2-(trimethylsilyl)ethoxymethyl (SEM) 6–8,57, 88, 90, 99, 107, 192–193, 200, 209,258, 312–314, 345, 367, 375, 401, 422,433, 436, 443, 471, 477, 529, 536–539,

Index 677Protecting Groups Third Edition by Philip J. Kocieński

554–555, 557, 563, 575, 596, 606,626–627

N-(2-trimethylsilylethoxy)methyl 2582-(trimethylsilyl)ethoxymethyl chloride 6262-(trimethylsilyl)ethoxymethyl esters 4282-(trimethylsilyl)ethyl ester 5342-(trimethylsilyl)ethylsulfonyl (SES)

554–558, 606–609, 627trimethylsilylethynyllithium 34N-trimethylsilylimine 5983,6,6-trimethyl-1,5,6,7-tetrahydro-4H-inda-

zol-4-one 606trimethylstannyllithium 65trimethylvinylsilane 5572,4,6-trinitrotoluene 1351,3,5-triols 153triphenylcarbenium tetrafluoroborate 157,

267, 322triphenylcarbenium triflate 274triphenylmethanesulfenamides 559–560triphenylmethanesulfenyl chloride 560triphenylmethanethiol 373triphenylmethanol 373triphenylmethyl (trityl) 37, 269–275,

371–374, 585–591N-triphenylmethyl 37, 133, 216, 329, 371,

382, 408, 459, 506, 508, 585–586triphenylmethyl bromide 589triphenylmethyl cation-promoted benzyl-

ation 256triphenylmethyl chloride 273, 374, 589triphenylmethyl esters 414triphenylmethyl ethers 5, 81, 288,triphenylmethyl hydroperoxide 66triphenylmethyl tetrafluoroborate 291triphenylmethylamine 586triphenylmethylamine as an ammonia

equivalent 586triphenylmethylpyridinium fluoroborate

274triphenylphosphine 612triphenylsilane 229, 373triphenylsilyl chloride 229triphenylsilylthiol 373tris-(4-benzoyloxyphenyl)methyl

ethers 273tris(dibenzylideneacetone)dipalladium 420tris[4-(4,5-dichlorophthalimido)phenyl]-

methyl 273tris(dimethylamino)sulfonium difluorotri-

methylsilicate 209, 434

tris-(dimethylamino)sulfonium difluorotri-methylsilicate 169, 236, 274, 491, 509, 617

tris(2,6-diphenylbenzyl)silyl esters 440tris(4-levulinoyloxyphenyl)methyl 273tris(4-methoxyphenyl)phosphine 21tris(methylthio)methyllithium 106tris(pentafluorophenyl)borane 229tris(phenylthio)methyllithium 106trisodium 3,30,300-phosphinetriyltribenzene-

sulfonate 421, 526tris[triphenylphosphine]rhodium(I) chlor-

ide (Wilkinson’s catalyst) 12trityl, see triphenylmethyltryptophan 520, 548, 622, 625Tunicamycin 149, 207, 302, 346twist-boat conformation 132tyrosine 39, 239, 326, 461, 506

UDP-N-acetylmuramyl-pentapeptide 437,499

ultrasonication 126, 150, 237, 296, 341, 546Umpolung 78uracil 559, 565urethanes 5uridine 160, 560Ustiloxin D 550

valine 552Vancomycin 208, 210, 231, 281, 300, 346,

418, 582Varacin 367Verrucarin A 433Verrucarin B 345, 433Vincadifformine 551Vincamine 404, 588Vineomycinone 244vinyl acetate 327vinyl pivalate 332Vitamin D 67, 70Vitamin E 69von Braun degradation 575

Wacker oxidation 23, 97water 277wheat germ lipase 17, 330Wieland-Miescher ketone 60Wilkinson’s catalyst ([Ph3P]3RhCl) 276, 592Wilkinson’s catalyst, rearrangement of

allylamines to enamines 592Williamson ether synthesis 235, 253ent-WIN 64821 574

678 Index

Protecting Groups Third Edition by Philip J. Kocieński

9H-xanthen-9-yl 371xanthen-9-ylidene 160xylitol 163o-xylylene N,N-diethylphosphoramidite

464

Yamaguchi esterification 409, 438ytterbium(III) triflate 334

Zampanolide 258, 536Zaragozic Acid 140, 229Zaragozic Acid A 190–191, 295, 416Zaragozic Acid C 191, 403

zinc 176, 341, 343, 382, 414, 497, 540, 565zinc bromide 76, 88, 270–271, 296, 508zinc carbenoid 68zinc chloride 91, 150, 237, 248, 296, 538zinc in acetic acid 8, 424, 430, 553, 607zinc iodide 90, 95, 296zinc nitrate hexahydrate 123zinc triflate 90, 140zinc–copper couple 8zinc–lead couple 540zinc–silver couple 24zirconocene dichloride 103Zoapatanol 213

Index 679

Protecting Groups Third Edition by Philip J. Kocieński