Index

A Alkenylmetals, 38 Acetophenones, 10 Alkenylsilanes, 18 Horner–Emmons olefination, 7 Alkenylstannanes, 18 Acrylonitrile, Z-selective cross metathesis, 46 α-Alkoxycyclopentenone, 25 Acylgermanes, 18 (E)-β-Alkoxy divinyl ketones, 25 Acyl phosphonates, olefination, Co(TPP), 160 α-Alkoxyketones, 12 Acylsilanes, 18 Alkyl aryl ketones, 16 Acylstannanes, 18 Alkylidenephosphoranes, olefination, 208 Africanol, 187 Alkynes, conjugated dienes, 98 Aldehydes, 197 Z-alkenes, 40, 43 Fe(II)(TTP), olefination, 151 hydrofluorination, 60 Mo-based catalytic olefination, 149 hydrofunctionalizations, 134 MTO-catalyzed olefination, 149 hydrometalation, 43 olefination, 6 2-Alkynoate, conjugated dienes, 109 diazocarbonyl reagents, 161 Alkynoates, 108 oxygen-substituted phosphorus Alkynyl ketones, 16 ylides, 156 Allenamides, 126 Ph3As, 157 Allenoates, 108 Rh-catalyzed methylenation, 157 one-pot Wittig reaction, 213 Ru-catalyzed olefination, 157 Allylation, 54 Aldimines, olefination, 28 Allyl ethers, chiral, 258 Alkaloids, 171 N-Allylhydrazones, 107 Alkene cross metathesis, 178 Allylic alcohols, trisubstituted, 207 Alkene metathesis, catalytic Allylic carbonates, one-pot Wittig enantioselective, 187 reaction, 213 catalytic Z-selective, 189 Allylic gem-difluorides, 67 selective, 163 Allylic substitution, 54 selective relay, 174 Allylidenetriethylphosphoranes, 205 Alkenes, 197 Allylsulfides, multisubstituted, synthesis, 239 desulfurization, 16 tetrasubstituted, 1 Amino acid, (Z)-fluoroalkenyl moiety, 83 Z-Alkenes, stereoselective synthesis, 33 α-Aminoketones, 14 Alkenylboronic acid, fluorination, 62 Amphidinolides, 165 Z-Alkenyl chlorides, 47 Ando modification, HWE reaction, 223 Alkenylgermanes, 18 Anominine, 178 Alkenyl halides, trisubstituted, 209 Antiangiogenic triterpene, 9 Z-Alkenyl iodides, 35 Archangium gephyra, 174

271 272 Index

Archazolids, 119, 120, 174 Carbonyls, selective olefination, 1, 8, 34, 147 2-Arylacylates, 251 Cascade reactions, 163 Aryl alkyl acetylene, regioselective C–C double bonds, 148 hydrofluorination, 61 C–C triple bonds, reduction, 17 1-Aryl-2-alkyl-1-bromo-2-fluoroethenes, 79 Chinensiolide B, 170 Aryl boronic acids, 260 Z-Chloroalkenes, 47 4-Arylchromenes, 253 Claisen rearrangement, Lewis acid Aryl nonaflates, 259 promoted Z-selective, 55 Aryl sulfonates, 257 Clavukerin A, 181 Asperpentyn, 183 Cobalt catalysis, 159 Aspidosperma alkaloids, 187 Condensation, 59 Azaphosphetane, 227 Copper catalysis, 160 Aziridines, one-pot Wittig reaction, 214 Cross-coupling, 33, 59, 71, 239 Pd-/Ni-catalyzed, 38 B Cross metathesis, 49 Cyanthiwigins, 183, 184 Baconipyrone C, 188 Cyathin diterpenoids, 183 Barton–Kellogg olefination, 241 Cyclobutenes, electrocyclic ring-opening, 11 Baylis–Hillman cyclization, 37 ROCM, 46 Benzaldehyde, olefination, Cyclopropenylmethyl acetates, 139 metalloporphyrins, 152 1-Cyclopropylallenes, halohydroxylation, 139 Benzophenones, 10 Cylindramide A, 185 Benzothiazolyl sulfone, fluorinated, 64 2-Benzylidenecylopropyl-carbinols, 117 Benzylidenetriethylphosphoranes, 205 D Betaine, 206, 228 Decahydroquinoline, 181 Bis(diphosphinyl)butadienes, 136 Deoxpukalide, 165 Bis(trimethylsilyl)ketene, 3 Dialkyl(fluoroalkenyl)borane, 82 Bis(o-anisyl)phosphine oxide, 225 Diarylcycloalkylidenes, 250 Bis(o-alkylphenyl)phosphonoacetates, 223 Diazo reagents, 147 Bis(trifluoroethyl)phosphonoacetates, 221 Dibenzylphosphole oxide, 225 Bis(trifluoroethyl)phosphonoesters, 36 Dibromo esters, 5 Bissilylbutadienes, 95 Dibromofluoromethyls, reductive Bissilyloxyketene acetals, 122 dehalogenation, 70 Bistramide A, 178 Dibromo-2-fluoro-1-tolylethyl benzoate, 70 Blechert’s catalyst, 165 1,3-Dienes, 11, 87, 94, 258 Bongkrekic acid, 6 conjugated, 87 4-Bromobut-1-en-3-yne, 91 stereoselective synthesis, 87 Bromodiene/amide, 133 Dienoic esters, 160 4-Bromo-1,3-enyne, 91 (Z)-2,5-Dienol, 91 1-Bromo-1-fluoro-1-alkene, 72 Dienol phosphates, 96 BT-sulfone, 64 Dimethylvinylsilanol, 96 γ-Butenolides, 14 Dipeptide mimetics, 2 tert-Butyl phenyl ketone, 7 Diphenyldichalcogenides, 133 γ-Butyrolactams, 15 1,1-Diphenylethylene, 148 Discodermolide, 35 C Diynes, Yb-catalyzed hydrophosphination, 137 α-Dodecylthioketones, 15 C18(plasm)-16:0 (PC), 190 Carbene-copper complexes, N-heterocycle, 161 E Carbenes, 139, 147 Efomycine M, 119 Carbene transfer, one-pot Wittig reaction, 215 Electrocyclic reaction, 1 Carbon nucleophiles, 197 Elimination, 59 Index 273

Ene–ene coupling, 87, 110, 112, 131 H Ene–ynamide, RCM, 134 Halichlorine, 119 Ene–yne coupling, 87, 110, 113, 131 Harveynone, 183 Ene–yne macrocyclization, 103 Heck–Mizoroki coupling, 110 Ene–yne RCM, 179 Hell–Volhardt–Zelinski reaction, 4 Enolates, 3, 83, 222, 266 N-Heterocyclic carbene (NHC), 52, 67, 189 Enol ethers, 23, 25, 251, 252 Hexaisopropyltriphenoxide (HIPTO), 49 Enones, 16, 110, 254, 258, 265 Horner–Wadsworth–Emmons reactions, 3, 6, Enynes, 17, 47, 90, 177, 186, 262 36, 62, 197, 219 Epimeloscine, 173 Still–Gennari modification, 36 Epixanthatin, 186 Horner–Wittig reaction, 224 Epothilones, 51, 190 Hoveyda-Grubbs’s catalyst, 165 Epoxides, α-lithiated, 106 Hydrazones, one-pot oxidation, 242 Epoxyquinoids, 183 Hydroboration, 44, 90, 135 Erythrina alkaloids, 181 Hydrofluorinations, 59 Erythroidine, 181 Hydrophosphination, 136 Ester carbonyl, olefination, 24 Hydrosilylation, 44, 89, 95, 134 Ester enolates, 4 Esters, olefination, 23 I Ethylenediamine, 41 Ethyl(N-sulfinyl)iminoacetates, 94 Iejimalide B, 169 Ethyl(E,E)-2-methyl-6-hydroxysorbate, 111 Imines, 197 Ethyl 3-phenylpropionate, 25 olefination, 227 Evans–Akiba reaction, 197, 226 Iodoxybenzoic acid (IBX), 209 Iridium catalysis, 160 Iron(II) meso-tetra(p-tolyl)porphyrin (TTP), 151 F Iron(II) porphyrin, 148 Fe(TPP)Cl, 152 Isoclavukerin A, 181 Fluoroalkene dipeptide isosteres (FADIs), 67 Isodomic acid G, 2 Fluoroalkenes, [3.3] sigmatropic Isolaureatin, 177 rearrangement, 83 Isolysergol, 171 stereoselective synthesis, 59 Isomerization, 87 (2-Fluoro-1-alkenyl)iodonium salts, 75 Isoxazolyllithium, 3 Fluoroalkenylmetal, 59 (1-Fluoro-1-alkenyl)metal reagents, 74 (2-Fluoro-1,2-dialkylethenyl)boronates, 82 J (Fluorodienyl)boronate, 78 Julia olefination, 4, 7, 63, 137, 233, 242, 266 Fluorohaloalkenes, 59, 71, 75, 79 1-Fluoro-1-iodo-4-phenyl-1-butene, 72 Fluoro–Julia olefination, 63 K (Z)-1-Fluoro-2-(p-tolyl)vinyl benzoate, 70 Kainoid amino acids, 2 Fluoro-α,β-unsaturated carboxylic acids, 220 Kempenes, 182 (E)-α-Fluoro-α,β-unsaturated ester, 62 Kendomycin, 167 2-Fluorovinyl tosylate, 71 Ketenes, 4 asymmetric olefination, 155 F4t-neuroprostane, 42 Ketones, 197 MTO-catalyzed olefination, 150 G olefination, 7 Germalactones, 20 Rh-catalyzed methylenation, 158 Germanes, hypervalent, 20 KRN7000, 50, 190 Gigantecin, 185 Globostellatic acid, 9 Gramine, one-pot Wittig reaction, 214, 216 L Grob fragmentation, trisubstituted Z-alkene, 54 γ-Lactams, 15 Grubbs catalysts, 164 γ-Lactones, 14 274 Index

Laulimalide, 40 Oximidine III, 175 Lepadins, 181 Oxopolyene macrolide, 179 Lindlar reduction, 33 Lindlar’s catalyst, 40 Lithium diisopropylamide (LDA), 201 P Lycoflexine, 186 Palladium–vinyl bond, 260 Lycopodium alkaloids, 186 Peloruside A, 175 2-Phenylthiocycloalkanones, 15 α-Phenylthioketones, 15 M Phosphine oxides, 36 Macrocycles, Lindlar reduction, 40 removal, 216 Meloscine, 173 Phosphines, E-selectivity, 156 Mesotetraphenylporphyrin iron chloride tertiary, 147 (ClFeTPP), 154, 216, 244 1-Phosphinyl-1,3-dienes, 136 Metal carbenes, 239 Phosphonium ylides, 197, 227 3-(Methoxycarbonyl)-1,2-allen-4-ol, 139 Phosphorane, 151 N-o-Methoxyphenyl aldimines, 28 Phosphorus-stabilized carbon nucleophiles, 197 α-Methoxy phosphonium salts, olefination, 206 Phosphorus ylides, 34 4-Methyldienoates, 119 Photochromism, 2 α-Methylene cyclopentenoids, 26 Photoswitches, 2 Methyltrioxorhenium (MTO), 148 Pinnaic acid, 119 Molybdenum adamantylimido complexes, 190 Pinnatoxin, 168 Molybdenum catalysis, 148 Plasmalogen phospholipid, 50 MOM ester, 6 Polyanthellin A, 171 Monofluoroalkenes, 59 Polyenes, Still–Gennari modified HWE Morita–Baylis–Hillman reaction, 121 olefination, 37 Mo-/W-alkylidene monoaryloxide pyrrolide Poly-halo compounds, 67 complexes, 48 Polyketide, 174 Mucocin, 175 Porothramycins, 120 Mycale hentscheli, 175 Propargyl carbonates, 101 Propargylic esters, 127 Pseudotabersonine, 173 N Psilostachyin C, 170 Nakadomarin A, 191 Pyridinium chlorochromate (PCC), 209 Nazarov reaction, 25 p-Nitroacetophenone, 10 Norbornadiene, ROMP, 49 Q Norfuorocurarine, 120 Quebrachamine, 187 Norhalichondrin B, 179, 180

R O Relay ring-closing metathesis (RRCM), 174 Olefination, 1 Rhodium catalysis, 156 selective, 147, 197 Ring-closing alkyne metathesis (RCAM), 41 Olefins, metathesis, 33, 118 Ring-closing metathesis (RCM), 45, 164, 165 Z-selective, 45 Ring-opening/cross-metathesis (ROCM), 45 tetrasubstituted, 7 oxabicycle, 190 Organocatalysis, 87 Ring-opening metathesis (ROM), 183 Oxacyclononene, 170 RK-397, 179, 180 Oxaphosphetane, 38 Rollinia mucosa, 175 Oxarhodacycloheptadiene, 100 Ru(TPP)(CO), 152 Oxarhodacyclopentene, 93 Ru–carbene, 52 Oxetenes, electrocyclic ring-opening, 11, 30 Ruthenium catalysis, 157 Index 275

S Triethyl 2-fluorophosponoacetate, Schrock–Hoveyda catalyst, 172 HWE reaction, 62 Schrock’s catalyst, 165 Trifluoroacetophenone, 151 Secondary orbital interaction, 1 Trifluoromethyl ketones, 153 Selective relay alkene metathesis, 174 Trimethylsilyldiazomethane, 152 α-Selenoketones, olefination, 14, 16 Trimethylsilylynolate, 3 Silalactones, 20 Triphenylphosphine, 109, 117, 147, 213, 215 Silicones, hypervalent, 20 Triphenylphosphonium ylides, 201, 205, α-Siloxy ketones, 13 227, 230 Silylcyclobutenes, 18 Tris(2-methoxymethoxyphenyl)phosphonium Silyloxetenes, 18 ylides, 203 Sodium hexamethyldisilylamide (NaHMDS), 201 Spirophosphoranes, pentacoordinated, V olefination, 227 Vedejs model, 201, 242 Stelletta globostellata,9 Vigularia juncea, 170 Stemona alkaloids, 2 Vigulariol, 170 Still modification, HWE reaction, 221 Vinyl ethers, 50 N-Sulfonyl aldimine, olefination, 29 Vinylzinc, 73, 90, 98 Sulfonyl imines, 36, 228

W T Wittig reaction, 34, 136, 199, 244 Takai olefination, 138 catalytic, 218 Tamoxifen, 2, 22, 23 one-pot, 209 Tandem Wacker-type oxidation, 159 Schlosser modification, 206 Tebbe reagents, 23 Tetra(p-chlorophenyl)porphyrin iron chloride (Fe(TCP)Cl), 154, X 216, 244 Xanthocidin, 26, 27 Thiochromenes, 253 Thio esters, homologation, 24 α-Thioketones, 14 Y Torquoselectivity, 1, 10 Ynamides, carbozincation, 134 N-Tosylhydrazones, Yne–yne coupling, 87, 132 cross-coupling/olefinations, 239 Ynolates, 1, 3 Transition metals, 87 Ynol tosylates, 3 Transition metals, catalysis, 147 α-Trialkylsiloxy cyclic ketones, olefination, 14 Tricholomenyn A, 183 Z Triethyl 2-acyl-2-fluoro-2-phophonoacetate, 62 Zincke salt/aldehydes, 118, 119