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Abramov‐Type Phosphonylation of Aldehydes 389 Acetonitrile 102, 105, 157, 369, 443 Achiral Cyclic Ketones 371 Achiral Methyl K

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Abramov‐Type Phosphonylation of Aldehydes 389 Acetonitrile 102, 105, 157, 369, 443 Achiral Cyclic Ketones 371 Achiral Methyl K 533 Index a trialkylsilyl ketene acetals 379–382 Abramov‐type phosphonylation of aliphatic aldehydes 10, 11, 61, 67, 366, aldehydes 389 368, 369, 373, 376, 379, 385–388, acetonitrile 102, 105, 157, 369, 443 391, 395 achiral cyclic ketones 371 alkene hydrosilylation 57, 89–90, 421, achiral methyl ketones 371 429, 431, 432, 450 acid‐catalyzed indole silylation 223 primary and secondary hydrosilanes activated substrate interaction, externally alkoxyhydrosilanes 427 coordinated‐nucleophile hydrosilanes 427 direct aldol addition, of activated monohydrosilylation 427 thioesters 395–396 platinum‐catalyzed hydrosilylation, enantioselective Morita–Baylis– chlorohydrosilanes 427 Hillman reaction 396–397 TOF 428 acyclic nucleophiles 371 alkene isomerization 250, 433 acylhydrazono esters, allylation alkenylsilanes 18, 288, 294, 296, 298, of 361 299, 303, 519, 521 acylsilanes 11 alkenylsilanols 292 adamant‐1‐yl methyl ketone 451 alkenyl[tris(trimethylsilyl)] agostic bis(silyl) hydridorhodium(III) silanes 275 complex 444 alkoxide base‐catalyzed silaboration, of aldehyde‐derived trichlorosilyl enol aromatic alkenes 24 ethers 375 alkoxyhydrosilanes 418–427 aldehydes, allylation of 3, 336, 1‐alkyl‐1’‐arylethylenes 430 362–364, 366, 368, 369, alkyl chloro silyl ether 366, 376 375–378 alkylsilanes 241, 263, 265–267 aldol addition 371–373, 375, 378–386, alkynyltrimethylsilanes 308 391, 393–396 allylacetone 454 aldolization process 371, 373 allylating reagent 366, 376 aldol reactions allylation of aldehydes 3, 336, preformed enoxysilane 362–364, 366, 367, 375–376 derivatives 371–375 allylation, of benzaldehyde 3, 336, trialkylsilyl enol ether 362–364, 366, 368–370, derivatives 378–379 376–378 Organosilicon Chemistry: Novel Approaches and Reactions, First Edition. Edited by Tamejiro Hiyama and Martin Oestreich © 2019 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2019 by Wiley-VCH Verlag GmbH & Co. KGaA. bindex.indd 533 01-10-2019 14:34:24 534 Index allylation of substrates arene‐arene interactions 340 allylic trichlorosilanes arene borylation 446 allylation, of C=N aromatic aldehydes 4, 336, 363, 369, bonds 359–361 375, 376, 379, 381, 385, 387, 388, allylation, of C=O 390, 395, 396 bonds 361–371 aromatic C–H silylation 218 allylation of trichlorosilanes 361 aromatic ketimines 342 allylation reaction 361, 365, 366, 369, aromatic N‐alkyl ketimines 345 370, 377, 382 aromatic N‐aryl ketimines 345 allylic alcohol 304, 361 aryl‐HOMSi reagents 313, 315, 317, 319 allylic amines, formation of 361 arylmethylamines 346 allylic nitriles 387 arylpropylsilole derivatives 196 allyl silanes 241, 245, 250, 252 aryl(trimethyl)silanes, desilylative formation 421 acetoxylation of 313 allyltributylstannane 376 asymmetric catalyst efficiency allyltributyltin 336, 375 (ACE) 344 allyltrichlorosilanes 336, 359–364, asymmetric Diels–Alder reaction, with 366, 369–371, 376 silylnitrilium ion 156, 157 to aldehydes 363 asymmetric Hosomi–Sakurai with N‐oxides 369 reaction 166–167 allyltrifluorosilanes 361, 362 asymmetric hydrosilylation 428, 430 allyltrimethoxysilane 360, 361 asymmetric hydrosilylative reduction of α,β‐unsaturated aldehydes 4, 5, 371, ketones 44 387, 394β asymmetric imine reduction 346 α,β‐unsaturated ketones 68, 385, 387, asymmetric Mukaiyama–Michael 394 reaction 164 (E)‐α,β‐unsaturated nitriles 387 asymmetric silylation protocol 461, α‐chloroimines 342 479 α‐hydroxy amides 387 asymmetric synthesis, of chiral silicon α‐hydroxylsilanes 9–11 molecules 503 α‐hydroxy oxime ethers 488, 491 desymmetrization α‐substituted phosphonyl dihydrosilanes 506–515 compounds 389 of prochiral silicon α‐substituted trimethylsilyl enol atoms 503–506, 513–515 ethers 379 atoms in molecules (AIM) 335, 336 (aminomethyl)pyridine cobalt(II) α‐trichlorosilyloxy phosphonate 390 dihalide 426 auxiliary based kinetic resolution ammonia‐borane (NH3BH3) 454 strategy 482 anilide moiety 340 axial chirality 369, 497 anionic radical α‐diimine ligands 427 anti‐homoallyl alcohol 361 b anti‐Markovnikov addition 422, 428, Bartlett‐Condon‐Schneider 429, 434 reaction 73, 75 anti‐Markovnikov hydrosilylation of base‐catalyzed C–H silylation alkenes 91, 426, 431 method 224, 230, 232–234 antimuscarinic agents 521, 527, 528 base‐metal catalysts, for alkenes Arbuzov‐type dealkylation 390 hydrosilylation bindex.indd 534 01-10-2019 14:34:24 Index 535 iron and cobalt catalysts binaphthyl‐based sulfur‐stabilized containing CO, CNR, and NHC silicon cations 158, 162 ligands 421–425 biomass conversion 48, 50 tridentate nitrogen redox‐active biphenyl‐silyl scaffold 216 ligands 419–421 biscarboline N,N‐dioxides 368 nickel catalysts 426–427 1,1’‐bis(diphenylphosphino)ferrocene B(C6F5)3‐catalyzed C–H (dppf) 284, 430 silylation 215–216, 220 bisphosphine oxide derivatives 346 BCF‐catalyzed hydrosilylative bisphosphinoxides 347 reduction, of carbonyl bisphosphoramides 359, 364–366, compounds 38 371, 376–378, 381, 385 BCF‐catalyzed hydrosilylative reduction bisphosphoramide‐SiCl4 of thioketones 42 complexation 378 BCF‐catalyzed silylative reductions with bis(imino)pyridine (PDI) 419–421, silanes 39 428–430, 434 BCl3‐catalyzed C–H silylation cobalt complexes 429 213–214 cobalt(I) complexes 420 benzaldehyde 361 iron(0) complexes 420 allylation 364, 366 bis‐silylene ligand 441, 443, 454 benzil, stereocontrolled hydrosilylative bis‐silylene with Ni(COD)2 441 reduction of 43 bissulfinimide 346 benzodiazepinones 344 bis[(trimethylsilyl)methyl]iron(II) benzoxazinones 344 complexes 420 benzoyl hydrazones 359, 361 borane catalyzed Si–H bond benzyldimethylsilyl‐based various activation 36–38 nucleophiles 299 borylation β‐amido enones 346, 347 of fluoro‐and trifluoroarenes 448 β‐aryl substituted β‐amino esters 350 of furan 448 β‐diketiminate silylene ligand 454 borylation, of pyridine derivatives 447 β‐enamino esters 344, 350 bromoacetophenone 441 β‐hydroxy activated thioesters 396 1‐bromo‐2‐(3‐bromopropyl) β‐hydroxy dimethyl acetal 379 benzene 483 β‐hydroxy esters 379, 381 Brønsted acid‐catalyzed β‐hydroxy trifluoroethyl enantioselective, silylations of thioesters 395 alcohols 479–481 β‐ketiminate cobalt(I) complexes 425 Brønsted base‐catalyzed C–H silylation, β‐phenethyl 422 of alkynes 226–229 β‐silicon stabilizing effect 34 Brookhart–Wei mechanism 97 BF3‐catalyzed hydrosilylation of Buchwald–Hartwig amination 449 carbonyl compounds 37 bulkiest catalyst 369 biaryl synthesis 274 butyl‐HOMSi reagent 318 bicyclic guanidines 460 bidentate bis(NHSi)‐ferrocene c ligand 454 carbocations 51, 56, 71, 73–75, 106, bidentate catalysts 339, 365 138, 515 bimetallic activation, of R2SiH2 432 carbon‐carbon bond formation, of β‐imino esters 346–347 Grignard reagents 442 bindex.indd 535 01-10-2019 14:34:24 536 Index carbon‐carbon bond‐forming chelation‐assisted C(sp3)–H silylation, reactions 397, 439, 441, of 2‐substituted pyridines 202 443–444 chelation‐assisted regioselective carbon‐carbon double bond 15, 381 silylation, of aryl C–H carbon‐heteroatom bond‐forming bonds 176 reactions 445–451 chiral aldehydes 375 carbon–nitrogen double bonds 338 chiral allenic bisphosphine oxide 357 carbon–oxygen double bonds 338 chiral bidentate phosphoramides 363 carbon‐phosphorus bonds 389 chiral Brønsted acid 479, 480 carbonyl compounds 371 chiral Brønsted base 467, 469 BCF‐catalyzed hydrosilylative chiral‐carbon‐free enantioenriched reduction 38 chiral silicon molecules 499 BF3‐catalyzed hydrosilylation of 37 chiral diamine 9, 361 Piers‘ seminal hydrosilylative chiral enolates 375 reductions 37 chirality 20, 22, 157, 166, 369, 495, reduction of 61 497, 498, 504 carbonyl hydrosilylation 92, 101, 118, chiral NHC‐catalyzed enantioselective 451 conjugate silylation 23 carboxy amide groups 342 chiral N,N’‐dioxides 375 catalytic asymmetric synthesis 430 chiral N‐oxides 368 catalytic C–H silylation chiral phosphoramide 359, 363, 366, Brønsted acids 222–224 507 Brønsted bases 224–229 chiral pyridine N‐oxides 370 Lewis acid 213–222 chiral silane 482–488 catalytic cyclotrimerization 444 chiral silicon molecules 495 catalytic dehydrogenative borylation, of vs. chiral carbon molecules 495 arenes 447 history 496–497 catalytic H/D exchange reaction 447 chiral siloxane 496 catalytic hydrosilylation, of C=O chiral silylguanidinium salt 461 bonds 91, 99, 102, 103, 119, chiral sulfinimides 346 120, 207, 314, 418, 434 chiral sulfoxides 369 catalyzed HSiCl3 imine reduction 351 chiral transition metal catalyst catalyzed silylation, of alcohols 459 promoted reactions 513–515 cationic iridium complex 94, 96 chlorosilanes 336, 483, 499, 500, 519, cationic silicon Lewis acids 142, 155, 522 159 C(sp3)–H silylation 198–207, 238 C=F bond activation 137 cinchona‐based picolinamide 347 cationic silylene complexes 91 classical Ojima mechanism 91 cationic trichlorosilyl species 376 Cleroindicin D, C, and F 467 C2‐/C3‐selective C–H silylation of Co(2‐ethylhexanoate)2 421 heteroarenes 190 (IPr)cobalt amide complexes 424 chair‐like arrangement 366, 373 cobalt catalysts 418–426 2‐ chalcone 157, 158, 160–163, 454 Co(I)[bis(imino)pyridine] 421 C–H bond functionalizations 200, 445 CO2 hydrosilylation 108 C(sp)–H bond silylation 171–174 cationic complexes 110 chelation‐assisted benzylic C(sp3)–H iridium complex 110 DIPP silylations 201 ( CCC)CoN2 424, 425 bindex.indd 536 01-10-2019 14:34:24 Index 537 condensative vinyl‐THP 52 cross‐coupling reactions, of conjugated N‐heterocycles organosilicon compounds hydrosilylation 104 alkenylsilanes 299 continuous flow reductions 349 alkenylsilanols 292 cooperative catalysis, at Ru–S alkyl(bis‐catecholato)silicates 282 bonds 127 allylsilane compounds 296–300
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