471 Index a – four-component reaction 462 acetic acid 26, 254, 279, 289, 290, 316, 425, 446 – primordial electrophilic activation of 346 acetonitrile 47, 93, 101, 114, 266, 267, 272, 280, aldehyde–indole condensation 352 389, 412 aldehydes 19, 26, 34, 42, 80, 87, 90, 92, 112, 130, acetylated carbohydroxylation product 403 133, 167, 225, 283, 293, 357, 415, 416, 1-acetylcyclopropanecarboxamides 119 429, 444, 458 acetylene carboxylates 351 – 1,3-dipolar cycloaddition of 454 acetylenedicarboxylates 351 – DMSO, oxidation in situ 384 acetylenes 333, 351, 368, 374 – four-component reaction 462 achiral and racemic multicomponent – lithium bis(trimethylsilyl)amide 326 reactions 111 – three-component cycloaddition of 455 – involving four reactive sites 139–142 – three-component reaction of 443 – involving one pronucleophilic reactive – trimethylsilylimines 326 site 111–115 aldol condensation 367, 368, 383 – involving three reactive sites 134–138 aldol reaction 115, 188, 195, 197 – involving two reactive sites 115–134 – three-component aldol-type reaction 463 acid chlorides 215, 343, 344, 354, 357 aldol-type product 416 – catalytic transformation of 342 alicyclic ketones 429 Acm-S-protected cysteines 244 aliphatic amines 90 acrolein 116, 149 aliphatic ketones 79 acrylate 184, 411, 419 alkaline Boc deprotection 339 acyclic alkanes 423 alkaloid-like polycyclic moieties 29 acyclic allenes 305 alkaloids 29, 121, 146, 162, 164, 176, 404, acyclic analogs 232 446, 455 acyclic anhydrides 395–398 alkaloid-type polycycles 162 acyclic/cyclic benzylamines 274 alkane carbonylation 421 acylamino-1,3-butadiene 26 alkenol partner, trapping of 417 acylhydrazine 422 alkenylidene oxazolidinones acyl iodide 421 – A3-carboxylative cyclization 337 1-acyloxy-1,3-butadiene derivatives 396 – four-component synthesis 337 N-acyloxyphthalimide 412 alkenynes carbocyclization 416 5-acylpyrid-2-ones alkoxyallenes 324, 326, 327 – coupling–amination–aza-annulation – three-component reaction 327 four-component synthesis 345 1-(alkoxyarylmethyl)indole-3-carboxyl – four-component synthesis of 345 esters 293 acyl radicals, nucleophilic reactivity 423 α-alkoxy-β-hydroxy esters 188 o-acyl-substituted cyclohexenes 26 2-alkoxyfuro[2,3-c]quinolines 286 α-adduct intermediate 275 alkoxyoxazoles 444 alcohols 346, 429, 433, 460–462 – three-component synthesis of 444 Multicomponent Reactions in Organic Synthesis, First Edition. Edited by Jieping Zhu, Qian Wang, and Mei-Xiang Wang. 2015 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2015 by Wiley-VCH Verlag GmbH & Co. KGaA. 472 Index alkoxy radical 426 – three-component synthesis of 364, 365 2-alkoxy-substituted 2,5-dihydropyrroles 326 – transition metal-catalyzed processes 333 6-alkoxy-tetrahydropyridines 122 alkynols 464 α-alkyl-α-diazoacetates 186 alkynones 342 N-alkyl amines, oxidation of 266 – catalytic generation of 341, 342 2-alkylamino-3-arylquinoxalines 288 2-(1-alkynyl)-2-alken-1-ones 208 – synthesis, postulated mechanism 288 2-alkynylanilines 293 2-[1-alkyl-5,6-bis(alkoxycarbonyl)-1,2,3, 3-alkynylated β-amino acid ethyl esters 4-tetrahydro-2-oxopyridin-3-yl]acetic acid – three-component synthesis 352 derivatives 390 γ,δ-alkynyl-β-amino acid esters α-alkyl diazoacetates 189 – Cu(II)-catalyzed three-component synthesis alkyl halides 117, 429 of 352 – abstract halogens 431 alkynyl benzaldehyde hydrazine – carbonylation 419 – Fischer carbene mediates a cyclization of 369 N-alkyl hydroxylamine 279 2-alkynylbenzaldehydes 283 alkylidenecyclopropanes 424 ortho-alkynyl benzaldehydes 349 alkylidene malonates 112 2-alkynyl benzaldehyde substrate 346 alkyl iodides 420 2-alkynylbiaryls 67, 68 – one-carbon homologation of 419 α-alkynyl enaminyl Pd species 339 2-(3-alkyl-4-oxo-2-thioxo-1,3-thiazinan-5-yl) α-alkynyl indoles 337 acetic acids – three-component synthesis of 338 – generation of 389 ortho-alkynyl phenyl isonitrile 348 – three-component synthesis 389 alkynyl sulfones 404 alkyl radical 422 allene reaction 322 alkyne 370, 422 allenes – 1,3-dipolar cycloaddition 357 – in heterocycles synthesis 301 – titanium-catalyzed four-component reaction – intramolecular Michael addition 303 of 370 – multicomponent reactions of 314 alkyne–imine MCRs 160 – palladium-catalyzed reactions 307, 308 alkynes 343 – reactions with acceptor-substituted – in cycloadditions 356 allenes 301 ––in Cu(I)-catalyzed 1,3-dipolar azide–alkyne –– catalyzed multicomponent reactions cycloaddition 358–366 316–318 –– dienophiles in MCRs 366–370 –– uncatalyzed multicomponent –– as dipolarophiles 356–358 reactions 318–323 – electrophiles, conversion 341–345 – reactions with donor-substituted – as electrophilic partners 351–356 allenes 301, 323–328 – as nucleophilic, electrophilic, dipolarophilic, – reactions with 1,2-propadiene 302 and dienophilic reaction partners 334 –– copper-, nickel-, and rhodium-promoted – as nucleophilic, exemplified reactivity multicomponent reactions 310–314 patterns of 334 –– multicomponent reactions without – π-nucleophilic reactivity 345–351 transition metals 314, 315 – σ-nucleophilic reactivity 335 –– palladium-catalyzed multicomponent –– alkyne–aldehyde–amine condensation– reactions 302–310 A3-coupling 335–337 α-allenic sulfonamides 306 –– alkyne–(hetero)aryl halide (sonogashira) allenic p-toluenesulfonamides coupling 337–341 – palladium-catalyzed carbonylation- –– electrophiles, acetylide additions 335 coupling-cyclization of 306 – organometallic MCRs, reaction rac-2,3-allenoates 455 partners 370–373 – 1,3-dipolar cycloaddition and kinetic – radical-mediated Cu-catalyzed three- resolution 456 component 366 allenoic acids 316 – terminal alkynyl C-H bonds 335 allenyl alcohols Index 473 – copper-mediated carbomagnesiation of 311 2-(1-aminoalkyl)-5-alkoxyoxazoles allenyl amidine 365 – Ugi-type three-component synthesis of 444 α-allenyl amines 2-(1-aminoalkyl)-5-aminoxazoles 443 – allenyl imine intermediates 310 α-amino amides 277, 412, 428 – palladium-catalyzed three-component – quaternary centers 429 cascade reaction 307 4-aminobenzo[b] [1,4]oxazepines allenyl imidothioate 324, 326 – three-component synthesis of 354, 355 allenyl imines 327 amino carbonyl compounds 273 1,2-allenyl ketones anti-β-amino carbonyls 440 – palladium-catalyzed carbonylative 2-amino-3,5-dicarbonitrile-6- dimerization of 316 thiopyridines 296 allenyl phosphonates 317 3-amino-3,4-dihydropyridinones 465 allenylsilane 315 amino esters – treatment 315 – 1,3-dipolar cycloaddition of 454 allyl acetoacetate 98 – three-component cycloaddition of 455 allyl chloride–aryne–alkyne coupling 60, 63 amino-functionalized ionic liquids 117 3-allyl N-cyanoindoles 348 2-amino-4-(5-hydroxy-3-methyl-1H-pyrazol- allylic alcohols 208 4-yl)-4H-chromene-3-carbonitrile allyl isocyanide 80 derivatives 138 π-allylpalladium species α-amino imides – cyclization of 310 – Ugi-type three-component reaction 277 – iodobenzene derivative, carbopalladation β-amino iso(thio)cyanates 17 of 303 α-aminomalonate 144 N-allylpyrimidines 103 5-aminooxazoles 244, 245 allyl-substituted hydroxypyrimidines 97 3-amino oxindoles 462 allyl sulfone 406 6-aminopenicillanic acid 4 allyl-tributylstannane 406 ortho-amino phenol 354 allyltrimethylsilane 395 – three-component synthesis of 354 Alternaria alternata 232 ortho-aminophenylacetylenes 368 alumina-promoted hydrolysis 287 4-amino-phthalazin-1(2H)-ones (APOs) 36 amide 277 – one-pot palladium-catalyzed MCR amidines toward 35, 36 – addition 423 5-aminopyrazole 21, 22 – formation 366 2-aminopyridines 292 – palladium-catalyzed synthesis 34 4-aminopyridines 84 amidinyl-substituted radicals 366 4-aminoquinolines 84 α-amido lactams α-amino-substituted alkoxyallenes 327 – oxidation–dehydration–Ugi reaction 273 4-amino-1,2,3,4-tetrahydroquinolines 447 amidomethyl-substituted 1,2,3-triazoles aminyl radicals 366 – three-component synthesis of 362, 363 ammonia 79, 94, 95, 109, 123, 126, 147, amido-substituted cyclohexadienes 367 386, 458 – substituted cyclohexadienes, pseudo-four- ammonium acetate 118 component synthesis of 367 – catalyzed, Hantzsch condensation reaction amines 26, 34, 36, 73, 90, 126, 222, 257, 305, of 459 389, 429, 430, 431, 432, 442 amphiphilic functionality, in situ – to 4CR products 387 generation 343 – four-component reaction 462 analgesic 393 – four-component reaction (4CR) 379 AnchorQueryTM 7 – Michael addition of 352 2- and 4-nitrophenols 78 syn-β-amino-αalkoxy esters 461 anellated azepines 357 aminoacetaldehyde dimethoxyacetal 96 anellated 4H-thiochromen-4-ones syn-β-amino-α-hydroxy esters 461 – three-component synthesis 343 1,2-amino alcohols 429 anellated isoquinolinium salts 346 474 Index angularly annulated furoquinolines – Diels–Alder adducts 390 – three-component synthesis of 369 β-aryloximes 403 anhydride-based multicomponent arylpalladium species 305 reactions 379 1-aryl-4-(2-phenylethynyl)[1,2,4]triazolo[4, anhydride used, in MCRs 3-a]quinoxalines – structures of 380 – four-component synthesis 339 anilines 188, 196, 464 N-aryl proline amides 30 – aldol-type reaction of 462 N-aryl-pyrrolidine-2-carboxamide 90, 91 – as amino substrates 335 N-arylpyrrolidine-2-thiocarboxamides 91 – aza-Diels-Alder reaction of 453 N-aryl thiocarboxamides 96 – Michael addition of 352 arynes 39 – three-component cycloaddition of 455 – based multicomponent reactions 41 – three-component reaction of 443 – 2,3-didehydrobenzofuran 39 annulated cyclohexadiene 372 – transition metal-catalyzed multicomponent annulated furoquinolines reactions 60 – ortho-aminophenylacetylenes 368 –– annulations 60, 61, 63–65 annulated hydroquinone 371, 372 –– cross-coupling-type reactions