417 Index Page numbers in italics refer to illustrations a – propargylation 125–127, 128 acetone – trifluoromethylation 131–133 – nitrobenzaldehyde reaction 361 aldol reactions – transformation to imines 352–355 – ammonium betaine catalysis 211–212 acetonitrile hydrolysis 229, 230 – ammonium bifluoride catalysis 214 acetophenone hydrogenation 68–69 – enamine-Lewis acid catalysis 133–136 acetylene hydroamination 192 – – bifunctional amine-boronic acid catalysts acid–base bifunctional group spacing 133, 134 352–356 – – bifunctional amine-metal Lewis acid acyl-transfer reactions 299 catalysts 133–134 alcohol dehydrogenase 330–331, 345 – – cooperative arylamine-metal Lewis acid alcohols catalysis 135–136 – amination 190–191 – – enamine addition to activated ynals – dehydrogenation 89–93 134–135 – formation 334 – Lewis acid–Brønsted base catalysis 7–8, – kinetic resolution 334–337 17–19 – oxidation 101, 102 – – ethyl diazoacetate 18 aldehydes – – isocyanoacetate 21 – addition to nitroolefins 298 – – thioamides 22, 24 – alkenylation 127–131, 132 – Lewis acid–Lewis base catalysis 47–48 – alkylation 39–40, 114–121, 126 – – Mukaiyama aldol reaction 47 – allylation 41–43, 115–125 – one-pot process 345 ––Michael/α-allylation cascade 119, 120 – solid surface catalysis 361–362 – – palladium(0)-Brønsted acid cooperative alkene hydrosilylation 96 catalysis 175–177 alkenylation, aldehydes 127–131 ––viaTsuji–Trostpalladiumπ-allyl alkylation 114–133 complexes 115–121 – aldehydes 39–40, 114–121 – arylation 131, 132 – ketones 39–40, 114–133 – benzylation 123–125 – phenylindanone 201, 202 – carbocyclization 127–130 – see also allylation; enamine-Lewis acid – cyanation 43–47 catalysis – – cyanoformylation 45–46 alkynes – – cyanophosphorylation 45–46 – activation 249–251 – – silylcyanation 43 – hydrogenation 288, 289 – cycloadditions 51–52 – hydrophenoxylation 240, 242 – enolization 22–23 allenes, gold-catalyzed hydroalkoxylation – glycolate aldol reactions 48 217–219 – hydrogenation 68 allenyne cycloisomerization 238–239 Cooperative Catalysis: Designing Efficient Catalysts for Synthesis, First Edition. Edited by René Peters. © 2015 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2015 by Wiley-VCH Verlag GmbH & Co. KGaA. 418 Index allylation 41–43 artificial metalloprotein 340–341 – aldehydes 41–43, 115–125 artificial oligopeptide catalysis 295 – – Michael/α-allylation cascade 119, 120 – nanosystems 312–320 – – via Tsuji–Trost palladium π-allyl – – dendrimer-based catalysts 312–315 complexes 115–121 – – nanoparticle-based catalysts 315–320 – chiral PTC/palladium catalysis 199, 200 – short peptides 295–307 –ketones 41–43 – – structures sequences 299–307 ––β-diketones 246–247 – – unstructured sequences 295–299 – – via Tsuji–Trost palladium π-allyl – supramolecular systems 307–312 complexes 116, 121–122 – – molecular aggregates 309–312 – palladium-catalyzed 219 – – unimolecular receptors/catalysts – – palladium(0)-Brønsted acid 175–179 307–309 allylsilanes 41 arundic acid synthesis 119 – activation 42 aryl chlorides, Negishi cross-coupling 242, α-aminosuccinimide production 238 243 α-cyanoacetate addition to vinylketones arylamines 113, 135, 137 235–236 – arylamine-metal Lewis acid catalysis alumina surfaces 366–369 135–136 – see also solid surface catalysis arylation, aldehydes 131, 132 aluminium-based catalysts aryldiazoacetate reaction 182 –Al-Li-bis(1,1′-binaphthoxide) (ALB) 8 asymmetric counteranion-directed catalysis – Al(Cl)–salen complexes 11 (ACDC) 117, 216, 218 – Al(III) salphen complexes 402 asymmetric Michael addition reactions amides 138–139 – N–H insertion reactions 184 ATANP artificial amino acid 303, 308 – Ru-amide complexes 69 Au catalysts see gold catalysts amination reactions 102–103, 104 aza-Claisen rearrangement 235, 247–249 – acetylene hydroamination 192 aza-nitroaldol (aza-Henry) reaction 16–17, – alcohols 190–191 20, 208–209, 212 amines azabenzonorbornadiene derivative – amine-chiral phosphoric acid combination ring-opening reaction 234 216, 217 aziridination, olefins 103, 104 – amine-thiourea catalysts 151–152, 207, aziridinium ring-opening reaction 219 208, 209, 382 – amine–Ru complexes 70–71 b – kinetic resolution 221, 337–338 Beller’s catalyst 78 amino acid ligand platform 17–20 benzofuran derivative synthesis 339–340 2-aminooxazoline synthesis 251–252 benzo[h]quinoline chlorination 231, 232 ammonia borane dehydrogenation 76 benzonitrile hydrogenation 74 ammonia synthesis 76–77 benzyl alcohol ammonium salt-based catalysts 205 – dehydrogenation 91 – alternative H-bonding donors 207–210 – oxidation 89 – ammonium betaine catalysts 211–212 benzylation, aldehydes 123–125 – ammonium fluorides 213–214 β-diketones, allylic alkylation 246–247 – – bifluorides 214 β-lactam synthesis 52–53, 54 – ammonium phenoxides 214–215 β-lactone synthesis 53–54 – bifunctional ammonium salt/Lewis acid β-sultam synthesis 56 catalyst 210 β-sultone formation 55 Amprenavir 214 betaines 211–212 annulation of homoenolates 56, 57 biaryl substrate resolution 296–297 arene imidation 252–253 biaryl-substituted secondary alcohol synthesis artificial enzymes 343–344 – design 305 bifunctional catalysis 112 – esterase mimic 308, 309 bimetallic catalysts 227–228 Index 419 – heterobimetallic catalysts 3–8, 20, 228, carbon–carbon bond formations 343, 345 246–258 – enantioselective 2 – – copper plus another metal 257–258 carboxylate ester cleavage 315 – – nickel plus another metal 255–257 (S)-carvone hydrogenation 282, 284 – – palladium plus another metal 246–255 cascade annulation reaction 129–130 – – silver plus another metal 257–258 CBS reduction 38–39 – homobimetallic catalysts 228–246 cellulose depolymerization 365 – – two gold centers 238–240 chalcone epoxidations 302 – – two iridium centers 243 chiral amine catalysts 113, 114 – – two nickel centers 242, 243 chiral ion-pairing catalysts 197–198 – – two palladium centers 228–238 – chiral anion-based catalysis 216–221 – – two rhodium centers 243–246 – – achiral organocatalyst/chiral anion – – two zinc centers 392–404 combination 216–217 ′ 1,1 -binaphthol ligand platform 3–10 – – chiral anion/achiral metal catalysis BINAP–Ru(II) complex 68 combination 217–219 BINOL-based cooperative catalysts 8–10, – – H-bonding catalysts 220–221 219 – chiral cation-based catalysis 198–216 biomass depolymerization 365–370 – – bifunctional 200–212 biphenyldiols 5 – – chiral cation-based bis-sulfonamides 384–385 ′ ′ catalyst/transition-metal catalyst 2,2 -bis(diphenylphosphino)-1,1 -binaphthyl combination 199–200 (BINAP) complex 41 – – with catalytically relevant achiral bis(imino)pyridine ligands 96 counteranion 212–216 borane-derived frustrated Lewis pairs see chiral ligands 113, 114 frustrated Lewis pairs (FLP) – bifunctional ligands 113, 115 boronic acids 131 chlorohydrin synthesis 233–234 – bifunctional amine-boronic acid catalysts chromium(III)–salen complex 409 133, 134 chromium(III)–salphen complexes “borrowing hydrogen” methodology 402–403 190–191 chromium(N )–salen complex 11 borylation 83 3 cinchona alkaloids 51–53, 145–148 Brønsted acids 171, 172 – as chiral organocatalysts 145–148, 149 – see also transition metal-chiral Brønsted acid cooperative catalysis – see also modified cinchona alkaloid Brønsted bases see Lewis acid–Brønsted base catalysts cooperative catalysis cinnamaldehyde dimerization 57–58 butenolide isomerization 163 class II aldolase activation 2–3 (Z)-2-butenyltrimethoxysilane 41 CO2 see carbon dioxide (CO2) cobalt catalysts c – Co(III)–nitrene radical complexes 103, C–H amination 102–103, 104 104 calixarene amines 360 – Co(II)–porphyrin complex 103 ε-caprolactone (CL) polymerization 379, cobalt–salen complexes 11–14 390 – dimeric 14 carbene catalysts 56–58, 377 – epoxide/CO2 copolymerization 402, carbocyclization, aldehydes 127–130 410–413 carbohydrate oxidation 332, 333 – kinetic resolution of epoxides 363–365 carbon dioxide (CO2) – – density effect 363–364 – activation 93,94 – – silica-tethered complexes 364–365 – electrochemical reduction 229, 231 – monomeric 12–14 – hydrogenation 75 – multimetallic 14 –polymerization 60–61 computational design 305 ––epoxide/CO2 copolymerization Conia-ene reaction 20, 258 390–413 cooperating ligands 67 420 Index cooperating ligands (contd.) – oxa-Diels–Alder reaction through – chemically active ligands assisting dienamine-metal Lewis acid catalysis metal-based catalysts 67–95 138, 139 – – with a pendant acid site 94–95 dienes, cycloaddition 96 – – with a pendant basic site 67–88, 95 dienolate intermediate 60 ––witharemotependantbasicsiteand dihydropyran derivatives 136 reorganization 89–94 3,4-dihydropyranone derivative synthesis – redox active ligands assisting metal-based 214–215 catalysts 96–103 dimethylaminoisoborneol (DAIB) 40 – – as electron reservoirs 96–100 dimethylaminopyridine (DMAP) catalyst – – direct substrate activation 101–103 374, 384 cooperative catalyst concept 1, 35, 172, 373 2,4-dinitrophenyl acetate (DNPA) hydrolysis copper catalysts 310 – copper complex-Brønsted acid cooperative direct alcohol fuel cells (DAFCs) 72 catalysis 188–189 direct aldol reaction see aldol reactions – Cu(II)–thiophenol complex 101 direct methanol fuel cell (DMFC) 77 – heterobimetallic catalysts 257–258 DNA cleavage 302, 303 cyanation 43–47 cyanoacylation 46–47 e cyanoformylation 45–46 electrophile activation 35–36, 37 cyanophosphorylation 45–46 enamine catalysis 111, 112 cyanosilylation 44, 45 enamine hydrogenation 276–277, 278 cyclization reactions 51–60 enamine-Lewis acid catalysis 112 –[2+2] cycloadditions 51–56, 96–97 – alkylation of carbonyl compounds –[3+2] cycloadditions 56–58