417 Page Numbers in Italics Refer to Illustrations

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 56–58 112–133 –[4+2] cycloadditions 58–60 – – alkenylation of aldehydes 127–131, 132 cyclodextrin-peptide hybrids (CD peptides) – – allylation of aldehydes 115–125, 126 308 – – allylation of ketones 116, 121–122 cyclohexene oxide (CHO) polymerization – – arylation of aldehydes 131, 132 61 – – enamine-iridium catalysis 122, 123 – – propargylation of aldehydes 125–127, –CHO/CO2 copolymerization 393–399, 406, 408–409 128 cyclopentane synthesis 129–130 – – triﬂuoromethylation of aldehydes 131–133 – asymmetric direct aldol reactions d 133–136 D-galactose oxidation 101 – – bifunctional amine-boronic acid catalysts dehydrogenation 133, 134 – alcohols 89–93 – – bifunctional amine-metal Lewis acid – ammonia borane 76 catalysts 133–134 – methanol 77–80 – – cooperative arylamine-metal Lewis acid δ-lactone production 59–60 catalysis 135–136 dendrimer-based catalysts 312–315 – – enamine addition to activated ynals diazadiene ligands 79–80 134–135 diazoacetophenone reaction 182 – asymmetric hetero-Diels–Alder reactions dibenzyl malonate addition to cyclic 136–138 enones 15 – asymmetric Michael addition reactions dicationic iridium(III) complex 89 138–139 Diels–Alder reactions 58–59, 136–138, – challenges 112–113 156–157 – classiﬁcation of catalytic systems 112 – asymmetric aza-Diels–Alder reaction enantioselective carbon–carbon bonding 2 (ADAR) 136–137, 138 enones – inverse-electron demand oxa-Diels–Alder – asymmetric hetero-Diels–Alder reactions (IED-HDA) reactions 136, 137 136–137 Index 421

– cyanide addition 255 formamides – epoxidation 205 – kinetic resolution 301 – hydrogenation 282 – transformation 255–257 – hydrosilylation/hydrogenation 278, 279 formic acid 77–78, 80 – organozinc reagent additions 257–258 free-OH-containing catalysts 201–207 enzyme catalysis 326 Friedel–Crafts reaction 155–156, 287 – enzyme-compatible metals 326, 327 frustrated Lewis pairs (FLP) 263–264 – metal-catalyzed in situ preparation of – enamine hydrogenation 276–277, 278 enzyme cofactor 328–332 – enone hydrogenation 282 – protoenzyme design 305 –H2 activation 263–264 – see also artificial enzymes; one-pot – – choice of Lewis acid 268–270 processes; specific enzymes – – choice of Lewis base 267–268 ephedrinium-based catalysts 204 – – intramolecular FLPs 270–273 (–)-epi-cytoxazone synthesis 181 – – mechanisms 264–267 epoxidation – heterocycle hydrogenation 279–281 – chalcones 302 – imine hydrogenation 273–276 – enones 205 – malonate hydrogenation 283–285 – farnesol 296, 297 – olefin hydrogenation 286–290 – olefins 296 – – nitroolefins 284–286 – one-pot process 339–340 – polycyclic hydrocarbon hydrogenation – quinones 204 288 – vitamin K3 203 – silylenol ether hydrogenation 278 epoxides – vinyl monomer polymerization – carbon disulfide reaction 50–51 385–390 –CO2 copolymerization 390–392 – – salen-type complex-based catalysis g 402–413 Ga-Li-linked-BINOL 10 – – zinc-based cooperative catalysis galactose oxidase (GOase) 101, 102 390–402 γ-lactam synthesis 57, 58, 255–257 –CO2 reaction 50, 51 glucose dehydrogenase 332, 333 – kinetic resolution 11–12, 14, 210–211 D-glucose oxidation 332 – – solid surfaces versus soluble molecular gold catalysts platforms 362–365 – allene hydroalkoxylation 217–219 –polymerization 60–61 – cooperation of two gold centers 238–240 ––asymmetric 14 – gold nanoparticle systems 316–319 – ring-opening reactions 11, 50–51, 402 – gold/palladium heterobimetallic catalyst ––meso-epoxides 15 249–251 esterase mimic 308, 309 – gold/palladium/Brønsted acid ternary , Et2Zn/(S S)-O-linked-BINOL cooperative system 179 catalyst 10 – gold(I)-amine catalysts 123, 125, 128 ethanol oxidation 72, 73 ethylene polymerization 96 h H-bonding catalysts 207–210, 220–221 f Heck reaction 233, 344–345 farnesol epoxidation 296, 297 helical peptide catalysts 302–303 FeFe hydrogenases 83, 84, 85 Henry reaction 17, 20 ferrocendiyl bisimidazoline – in a solid catalyst 359 pallada/platinacycle (FBIPP) catalyst – nitromethane 155 248–249 – pyruvate 155 ferrocene bisimidazoline bispalladacycle heterobimetallic catalysts 3–8, 20, 228, (FBIP) catalyst 235, 237–238, 246–258 248–249 – copper plus another metal 257–258 formaldehyde 77–78, 80 – Nd/Na heterobimetallic catalyst 20, 21 – hydrogenation 90 – nickel plus another metal 255–257 422 Index

heterobimetallic catalysts (contd.) – polycyclic hydrocarbons 288 – palladium plus another metal 246–255 – quinolone derivatives 278, 279 – silver plus another metal 257–258 – silylenol ethers 278 heterocycle hydrogenation 279–281 – transfer hydrogenation (TH) 69, 71, 1-hexene hydroformylation 244, 245 72–73, 74, 101 histidine 304 – ynones 182, 184 HIV-1 fusion process 305, 307 hydrolysis homobimetallic catalysts 228–246 – acetonitrile 229, 230 – two gold centers 238–240 – 2,4-dinitrophenyl acetate (DNPA) – two iridium centers 243 310 – two nickel centers 242, 243 – one-pot process 346 – two palladium centers 228–238 –urea 2 – two rhodium centers 243–246 hydrosilylation homoenolate annulation 56, 57 –alkenes 96 homogeneous–heterogeneous gap 351 –olefins 97 hydroboration 271–273 hydroxycyclopentadienyl ligand 89 hydroformylation reaction 244, 245 hydroxyketone kinetic resolution 298 hydrogen hydroxylactams, Pictet–Spengler type – activation by frustrated Lewis pairs reactions 221 263–264 – – choice of Lewis acid 268–270 i – – choice of Lewis base 267–268 imidazole/carboxylate cooperativity – – mechanisms 264–267 315–316 – cleavage 81–82, 83, 85, 93 imidazolidinone synthesis 251–252 – formation 84–88, 89 imines – oxidation 83–88 – alkynylation 187–189 hydrogen bonding-mediated cooperative – cyanation 43–47 organocatalysis 145 – cycloaddition reactions 52–53, 59 – highly enantioselective base organocatalysis – formation from acetone 352–355 145–151 – hydrogenation 189–190, 191–192 – modified cinchona alkaloid catalysts – – frustrated Lewis pair mediated 151–166 273–276 – – development as broadly effective – isomerization 164 bifunctional catalysts 153–159 – thiol additions 208 – – emergence as bifunctional catalysts – trifluoromethylation 215 151–152 in situ cofactor recycling 328–330 – – multifunctional cooperative catalysis –NAD(P)+ 328–330, 331–332 159–164 – NAD(P)H 328–331 hydrogen peroxide byproduct 331–332 InCl3/NEt3/BnOH catalytic system hydrogenases 80 377–379 – NiFe-hydrogenase 80,81–82 indoles, Friedel-Crafts reaction 155–156 hydrogenation 68–77 intermediate spin state 97 – alkynes 288, 289 inverse-electron demand hetero-Diels–Alder – carbon dioxide 75 (IED-HDA) reactions 136, 137 – enamines 276–277, 278 ion pairing 197 – enones 282 – see also chiral ion-pairing catalysts – frustrated Lewis pair mediated 273–290 iridium catalysts – heterocycles 279–281 – cooperation of two iridium centers 243 – imines 189–190, 191–192, 273–276 – iridium complex-Brønsted acid cooperative – ketones 68, 70, 74 catalysis 189–191 – malonates 283–285 iron complex-Brønsted acid cooperative – olefins 95, 245–246, 286–290 catalysis 191–193 – – nitroolefins 284–286 isatins, oxa-Diels–Alder reaction 138, 139 – one-pot process 342–343 isocyanoacetate, aldol reaction 21, 22 Index 423 isomerases 342–343 Lauryl-VVAGHH-C(O)NH2 peptide isomerization amphiphile 320 – imines 164 Lewis acids 35–36 – olefins 161–164 – activation 35–36, 37 – one-pot process 342–343 – arylamine-metal Lewis acid catalysis 135–136 k – bifunctional catalysts 210–211 ketenes, cycloaddition reactions 51–53, 59 – – amine-metal Lewis acid catalysts ketimine hydrogenation 274, 275, 276 133–134 ketones – dienamine-metal Lewis acid catalysis 138, – alkylation 39–40, 114 139 – allylation 41–43 Lewis acid–Brønsted base cooperative ––viaTsuji–Trostpalladiumπ-allyl catalysis 1, 2 complexes 116, 121–122 – hard Lewis acid–Brønsted base cooperative – asymmetric hetero-Diels–Alder reactions catalysis 3–20 136–137, 138 – – amino acid ligand platform 17–20 – cyanation 43–47 – – heterobimetallic catalysts 3–8 – – cyanosilylation 44 – – linked-BINOL-based 8–10 – hydrogenation 68, 70, 74 – – salen and Schiff base ligand platform – reduction 38–39, 330–331, 344–345 11–17 ketoxime transformation into amide 338 – in metalloenzymes 1–3 kinetic resolution – soft Lewis acid–Brønsted base cooperative – alcohols 332–337 catalysis 21–24 – amines 221, 337–338 Lewis acid–Lewis base catalysis 35 – epoxides 11–12, 14, 210–211 – alkylation 39–40 – – solid surfaces versus soluble molecular – allylation 41–43 platforms 362–365 – condensation reactions 47–48 – formamides and thioformanides 301 – cyanation 43–47 – hydroxyketones 298 – cyclization reactions 51–60 – one-pot processes 332–338 – epoxide ring-opening reactions 50–51 – – aqueous media 332–334 – ketone reduction 38–39 – – organic media 334–338 – Lewis acid and Lewis base activation – propylene oxide 12 35–38 – trans-(±)-N-(2-hydroxycyclohexyl)- – – modes of activation 35–37 acetamide 300 – – self-quenching 37–38, 39 – trans-cycloalkane-1,2-diols 299 – Morita-Bayliss-Hillman reactions 48–50 Kornblum–DeLaMare reaction 157 –polymerizations 60–61 – see also frustrated Lewis pairs (FLP) l Lewis bases 35, 36 L8-lysine transformation into L-pipecolic acid – activation 36–37 341 – see also Lewis acid–Lewis base catalysis La-NMe-linked-BINOL 10 ligands see cooperating ligands; specific La-O-linked-BINOL 10 ligands laccase-catalyzed oxidation 339, 340 lipase 334–338 lactam synthesis – β-lactams 52–53, 54 m – γ-lactam 57, 58 [M]-L-NH catalysis 83–88 lactide 375 [M]-L-OH catalysis 88, 89 – polymerization 61, 374–385 [M]-NH catalysis 68–80 lactones [M]-SR catalysis 80–83 – β-lactone production 53–54 MALDI (matrix-assisted laser – δ-lactone production 59–60 desorption/ionization) spectrum 376, – ring-opening polymerization 61, 100, 390 377, 379 lactonization 355 malonates 424 Index

malonates (contd.) – development as broadly effective – addition to chalcone 204, 206 bifunctional catalysts 153–159 – hydrogenation 283–285 – emergence as bifunctional catalysts – nitroalkene reaction 165 151–152, 153 malononitrile 360 – free-OH-containing catalysts 201–203 ′ Mannich reactions 48, 211 ––6-OH cinchona alkaloids 152, 157, D-mannitol synthesis 342–343 162, 202–203 mesoporous carbon materials 369 – multifunctional cooperative catalysis mesylate decarboxylative cross-coupling 159–164 253 – 9-thiourea cinchona alkaloid 157–159, metal catalysis 325–326 161 – chemically active ligands assisting molecular aggregates 309–312 metal-based catalysts 67–95 molecular hydrogel system 310, 311 – – with a pendant acid site 94–95 Morita–Baylis–Hillman reactions 48–50, – – with a pendant basic site 67–88, 95 148, 149 ––witharemotependantbasicsiteand morpholine-phosphoric acid combination reorganization 89–94 216 Morris catalyst 69 – chiral anion/achiral metal catalysis Mukaiyama aldol reaction 47 combination 217–219 –chiralcation-based n catalyst/transition-metal catalyst N-heterocyclic carbenes 56–58, 61 combination 199–200 N-thioacyl imines 59 – enzyme-compatible metals 326, 327 NAD(P)+ 328 – in situ preparation of enzyme cofactor – metal catalyzed in situ recycling 328–332 328–330, 331–332 – see also bimetallic catalysts; one-pot NAD(P)H 328 processes; transition metal-chiral – metal catalyzed in situ recycling 328–331 Brønsted acid cooperative catalysis; nanofiber technology 310 specific catalysts nanosystems 312–320 metalloenzyme reactions, Lewis – dendrimer-based catalysts 312–315 acid–Brønsted base catalysis 1–3 – nanoparticle-based catalysts 315–320 metal–salen complexes 11–16 naphthalene formation 240 metal–Schiff base complexes 15–17 Nd/Na heterobimetallic catalyst 20, 21 metathesis reaction 339–340, 346 Negishi-type cross-coupling reactions 99, methanol dehydrogenation 77–80 242, 243 methyl methacrylate (MMA) 385–390 nickel boratranes 95 γ-methyl-α-methylene-γ-butyrolactone nickel catalysts (γ-MMBL) 385, 389 – cooperation of two nickel centers 242, α-methylene-γ-butyrolactone (γ-MBL) 385, 243 388–389 – heterobimetallic catalysts 255–257 Mg(II)/Pd(II) heterobimetallic complex – NiFe-hydrogenases 80, 81–82, 84 253–254 – NiP4 85, 87 Michael additions 58, 235–238 nitro-Mannich reaction 20, 208 – α-cyanoacetates to vinylketones 235–236 nitroaldol reaction 3–5, 20, 213 – asymmetric 138–139 – ammonium bifluoride catalysis 214 – double addition 253–254 – anti-selective 14, 17, 20, 21 – malonate addition to chalcone 204, 206 – in a solid catalyst 359 Michael/aldol reaction cascade 165, 166 nitroalkene-malonate reaction 165 Michael/α-allylation cascade 119, 120 nitrobenzaldehyde Michael/carbocyclization cascade 130 – acetone reaction 361 modified cinchona alkaloid catalysts – malononitrile reaction 360 149–166 nitrogenase 80–81 – chiral PTC/palladium catalyst 199–200 nitromethane 213 Index 425

– Henry reaction 155 – Pd(II)-Brønsted acid cooperative catalysis nitroolefins 172–175 – aldehyde addition 298 – Tsuji–Trost allylation 115 – hydrogenation 284–286 – – aldehyde α-allylation 115–121, 118 – see also olefins – – ketone allylation 116, 121–122 “non-innocent” ligands 79–80, 94 phase-transfer catalysts (PTCs) 197–198 nucleophile activation 36, 37 phenylindanone alkylation 201, 202 2-phenylpyridine acetoxylation 229–231, o 232 olefins 94 phosphate cleavage 296, 319 – asymmetric isomerization 161–164 phosphino borane synthesis 271 – aziridination 103, 104 phosphonium salt catalysis 206–207, 209 – epoxidation 296 phosphoric acid catalysis 172–173 – hydrogenation 95, 245–246, 286–290 – iridium complex-phosphoric acid – hydrosilylation 97 189–191 – metathesis 339–340 – iron complex-phosphoric acid 191–193 – ring-opening polymerization 61 – palladium(0)-phosphoric acid 175–179 – see also nitroolefins – palladium(II)-phosphoric acid 172–175 one-pot processes 326–327 – Pd-Cu-chiral phosphoric acid catalysis – consecutive processes 339–347 217 – – consecutive mode 343–347 – rhodium complex-phosphoric acid – – tandem-mode 339–343 179–187 – metal-catalyzed in situ preparation of an – secondary amine-phosphoric acid enzyme cofactor 328–332 combination 216, 217 – metal-catalyzed racemization combined – silver complex-phosphoric acid 187–188 with stereoselective biotransformation pincer ligands 73–79, 91–93 332–338 polycaprolactone (PCL) 379, 390 – – aqueous media 332–334 poly(ethyleneimine) polymers (PEI) 356 – – organic media 334–338 polylactide (PLA) organocatalysis 111 – heterotactic 375, 377–378 organometallic fuel cells (OMFCs) 72 –isotactic 375, 377 oxaloacetate decarboxylation 301 – production 374–385 5-oxazolyl carbonate rearrangement 211 polymerization reactions 60–61, 373 oxetanes, asymmetric intramolecular – epoxide/CO2 copolymerization 390–392 ring-opening reactions 14 – – salen-type complex-based catalysis 402–413 p – – zinc-based cooperative catalysis palladium catalysts 390–402 – cooperation of two palladium centers – epoxides 60–61 228–238 – – asymmetric 14 – – enantioselective reactions 223–228 – ethylene 96 – – reactions with achiral or racemic – lactide polymerization 61, 374–385 products 229–233 – ring-opening polymerization (ROP) 374, – heterobimetallic catalysts 246–255 382 – – enantioselective reactions 246–249 – vinyl monomers with frustrated Lewis pairs – – nonenantioselective reactions 249–255 385–390 – one-pot processes 334, 343–345 – zwitterionic polymerization 376–377, – Pd-chiral anion combinations 217–219 385 – Pd-chiral phase transfer catalyst (PTC) poly(propylene carbonate) (PPC) 390–392, combination 199–200 404–405 – Pd-phosphane complex 344 PPNCl (bis-(triphenylphosphorylidene)- – Pd(0)-Brønsted acid cooperative catalysis ammonium chloride) 405 175–179 propargylation, aldehydes 125–127, 128 – Pd(0)/Au(I) catalyst 249–251 propargylic acid synthesis 134–135 426 Index

ProPhenol ligand platform 17, 18 s propylene oxide (PO) selenium-based molecular hydrogel system – copolymerization with CO2 390–392, 310, 311 402–413 self-quenching 37–38, 39 – hydrolytic kinetic resolution 12 short peptide catalysis 295–307 protoenzyme design 305 – structures sequences 299–307 pyrazol-5-one allylation 178–179 – unstructured sequences 295–299 pyruvate, Henry reaction 155 Shvo catalyst 89, 90 silica surfaces 357–358, 366–369 – carbamate thermolysis 357, 358 q – salicylaldehyde binding 357, 359 quinidine 145, 146 – see also solid surface catalysis quinine 145, 146 silver catalysts quinoline compounds – heterobimetallic catalysts 257–258 – hydrogenation 279, 280, 281 – – palladium/silver catalyst 252–253 – reduction 190 – silver complex-Brønsted acid cooperative quinolone derivatives, hydrogenation catalysis 187–188 278–280 – silver phosphate 219 quinone epoxidation 204 silyl nitronates, nitroaldol reaction 214 quinoxaline reduction 193 silylcyanation 43–45 quinoxalinone production 59 silylenol ether hydrogenation 278 size-exclusion chromatography (SEC) r 379 rac-cuspareine synthesis 279–280, 281 solid surface catalysis 351–352 rac-lactide polymerization 61, 374, 382 – alumina surfaces 366–369 redox switch 100 – depolymerization of biomass polymers relay catalysis 172 365–370 rhodium catalysts – kinetic resolution of racemic epoxides – cooperation of two rhodium centers 362–365 243–246 – mesoporous carbon materials 369 – in situ NAD(P)+ recycling 331–332 – silica surfaces 357–358, 366–369 – in situ NADPH recycling 330–331 – – carbamate thermolysis 357, 358 – Rh(I)–aminyl radical complex – – salicylaldehyde binding 357, 359 101, 102 – two-dimensional surface possibilities – rhodium complex-Brønsted acid 356–362 cooperative catalysis 179–187 soluble molecule catalysis 351–352 – rhodium-amino complexes 71–72 – acid–base bifunctional group spacing (R)−(–)-rhododendrol synthesis 345 352–356 rhomboid serine protease 310–312 spirooxindole tetrahydropyranones 138 ring-opening reactions Steglich rearrangement 211, 212 – azabenzonorbornadiene derivatives 234 stereodivergent dual catalysis 123, 124 – aziridinium 219 Stille coupling reactions 320 – epoxides 11, 50–51, 402 Strecker reaction 45 ––meso-epoxides 15 styrene hydrocarboxylation 217 – lactones 61, 100, 390 sulfene cycloadditions 54–55 – olefins 61 Suzuki cross-coupling reactions 233, 320, – oxetanes 14 343–344 – ring-opening polymerization (ROP) 374, synergistic catalysis 112 382 synthetic catalytic pores (SCPs) 309 ruthenium catalysts – metathesis reaction 346 t – Ru-amide complexes 69 Tamiflu synthesis 255 – Ru-diazafluorenide complex 93–94 taxol side chain synthesis 181 –Ru-pincercomplexes 91–93 teicoplanin A2-2 304–305, 306 Index 427 tetraallyltin 41–42 trimethylborane reaction with Lewis bases tetraamine tris(2-aminoethyl)amine (Tren) 264–265 308 O-trimethylsilylquinidine (TMSQD) 52, tetrahydrofuran (THF) 20 59–60 tetrahydropyran derivatives 136 O-trimethylsilylquinine (TMSQ) 52, 59 tetrahydroquinoline production 190 tryptophan radicals 101 thioamides TSNAVHPTLRHL peptide 320 – direct catalytic asymmetric aldol reaction Tsuji–Trost palladium π-allyl complexes 22, 24 115 – enolization 22–23 –aldehydeα-allylation 115–117, 118 thioformamides, kinetic resolution 301 – – asymmetric 117–121 thiourea catalysts 220–221 –ketoneallylation 116, 121–122 – thiourea-amine catalysis 151–152, 207, – – asymmetric 121–122 208, 209, 382 two-center catalysis 2 9-thiourea cinchona alkaloid 157–159, 161 – see also bimetallic catalysts Ti-Ga–salen complex 15 tyrosyl radical 101 Ti–salen complex 100 traceless dual activation catalysts (TDACs) u 239–240 urea hydrolysis 2 – test reactions for 240, 241 urease activation 2 trans-(±)-N-(2-hydroxycyclohexyl)acetamide, kinetic resolution 300 v trans-cycloalkane-1,2-diols, kinetic resolution valence tautomerism 98 299 vinyl monomer polymerization with transfer hydrogenation (TH) 69, 71, 72–73, frustrated Lewis pairs 385–390 74, 101 vitamin K3 epoxidation 203 transition metal-chiral Brønsted acid cooperative catalysis 171–172 w – copper complex-Brønsted acid 188–189 Wacker oxidation 345 – iridium complex-Brønsted acid 189–191 water, electrocatalytic reduction 97, 98 – iron complex-Brønsted acid 191–193 – palladium(0)-Brønsted acid 175–179 y – palladium(II)-Brønsted acid 172–175 ynals, enamine addition 134–135 – rhodium complex-Brønsted acid ynone hydrogenation 282, 284 179–187 – silver complex-Brønsted acid 187–188 z transition metal-chiral cation-based catalyst zanamivir, enantioselective synthesis 20 combination 199–200 zinc dicarboxylates 392 Tren (tetraamine tris(2-aminoethyl)amine) zinc-based catalysis 308 – epoxide/CO2 copolymerization 1,5,7-triazabicyclo-[4.4.0]-dec-5-ene (TBD) 390–402 , complex 410–411 –Et2Zn/(S S)-O-linked-BINOL cooperative trifluoroacetimidate rearrangement 235, catalyst 10 247–249 – Zn-dependent class II aldolase activation trifluoromethyl imine isomerization 164 2–3 trifluoromethylation 213 zinc-enolate generation 10, 18 – aldehydes 131–133 zirconium oxide catalyst 360 – imines 215 zwitterionic polymerization 376–377, 385