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Abnormal Addition-Elimination (Aea) Mechanism 360, 361 487 Index a arizonins B1 459 abnormal addition-elimination (AEa) arnottin 460 mechanism 360, 361 aroylacetonitriles 153 acetophenone-derived sulfonium salts 1-aroyl-3,4-dihydroisoquinolines 299 169 arylation reactions 17 acetylene dicarboxylates 171 9-aryldihydrophenanthrenes 15 actinorhodin 473 2-aryl-2H-indazole 74 acylalkylation, of arynes 126 aryl(mesityl)iodonium tosylate 320 9-acyl-9H-fluorenes 124 aryl ketone O-acetyloximes 215, 217 addition-elimination (AEn) mechanism 3-(arylsulfonyl)-2H-chromene-2-ols 360 168 addition-fragmentation reactions 455 aryl vinyl sulfides 102 AgF 183 aryne AgOTf-catalyzed reaction of amination reactions 114 2-alkynylbenzaldoximes with natural product synthesis 21 arynes 260, 261 possible reactivity modes of 13 3-alkoxy-2-naphthol 126 arylation reactions 17 alkynylbenzaldehyde 239 insertion reactions 17 alkynyllithium catalyzed aryne generation MCC 18, 19 326 molecular rearrangements 18–19 1-allyl-2-alkynylbenzene derivatives pericyclic reactions 14–16 227 transition metal-catalyzed reactions amino benzotriazole 11 18 aminocyanation, of arynes [2+2] aryne cycloadditions 30–31 with N-cyanoanilide 118 [2+2+2] aryne cycloadditions 31–32 aminosulfinylation, of arynes 114 [4+2] aryne cycloadditions 29–30 aminotriazole anion 389 aryne cycloaddition reactions 28 ammonium ylide 269 [2+2] aryne cycloadditions 30–31 aniline synthesis 111 [2+2+2] aryne cycloadditions 31–32 anthranilic acid derivatives 10 [4+2] aryne cycloadditions 29–30 aporphine alkaloids 464 aryne dipolar cycloaddition 69, 70 aquayamycin 467 aryne generation methods 28 aristolactam alkaloids 465 catalytic 323–326 Modern Aryne Chemistry, First Edition. Edited by Akkattu T. Biju. © 2021 WILEY-VCH GmbH. Published 2021 by WILEY-VCH GmbH. 488 Index aryne generation methods (contd.) Kobayashi’s fluoride induced aryne ortho-deprotonative elimination generation 12–13 aryliodonio group 321 methods of 9 HOTf 320 from anthranilic acids 10 LDAM 317, 319 deprotonation, of aryl halides 9 PhCl-LiTMP system 317, 318 fragmentation, of amino Uchiyama’s conditions 319 benzotriazoles 10 ortho-difunctionalized precursors HDDA 11 Knochel’s aryne precursors 323 metal-halogen exchange/elimination photoinduced aryne generation 10 methods 323 from ortho-borylaryl triflates silyl-based or OTf-based 11–12 difunctionalized aryne precursors Pd(II)-catalyzed C–H activation 322 strategy 12 Suzuki’s o-iodoaryl triflate 322 ortho-arynes strategy 316 of heterocycles 6–7 2,3-aryne intermediate 12 with substitution 5–6 aryne-mediated synthesis, of functional with oxaziridines 82 polyarenes photochemistry of 4 acenes, synthesis of 32–41, 43 transformations 128–129 carbon nanostructures 58–60, 62 aryne trifunctionalization 351, 353 helicenes, synthesis of 54–58 aryne-triggered rearrangements 267 perylene derivatives, synthesis of 43, aryne-triggered Sommelet–Hauser 46, 47 rearrangement of tertiary benzylic π-extended starphenes, synthesis of amines 271 48–54 aryne-triggered [1,2]-Stevens triptycenes, synthesis of 48 rearrangement aryne multifunctionalization benzylic thioethers 275 1,2-benzdiyne 336–342 of benzylic thioethers 276 1,4-benzdiyne 345–349 of tertiary amines 269 1,3-benzdiynes 342–345 1,2,3,4-tetrahydroisoquinolines 269, 1,3,5-benztriyne 349–351 270 benzyne insertion, C–H aryne-triggered [2,3]-Stevens functionalization cascade rearrangement 351–353 of allylic thioethers 277 aryne regioselectivity of cyclic allylic amines 273 electronic effect 330–335 of propargylic thioethers 276, 277 intermolecular aryne reactions 327 of tertiary allylic amines 272 small ring-fused arynes 335–336 of tertiary propargylic amines 274 steric effect 327–330 arynic triple bonds 36 arynes 1 arynophiles 111 characterization of 3–5 atomic force microscopy (AFM) 27 cycloadditions of 47 Au-bearing pyrylium cation 93 electrophilicity of 4 Au-catalyzed cyclotrimerization of arynes history of 1–3 197–198 Index 489 azacyclic allene 399 benzo[d][1,2,3]thiadiazole 1,1-dioxide aza-HDDA reaction 430 10 azanickelacycle 224 2,3-benzofuranyne 362–363 aza-ortho-quinone methides 162 4,5-benzofuranyne 78 2-azidoacrylates 98 benzo-fused carbocycles 1 azomethine imines 83 benzophenone O-perfluorobenzoyl azomethineylides 160 oximes 215, 217 benzothiadiazole dioxide 10, 11 b 2,3-benzothiophyne 361, 363 1,2-benzdiyne 1,2,3-benzotriazin-4-(3H)-ones 222 aryne trifunctionalization through benzoxaphosphole derivatives 175 Grob fragmentation 341 benzoxazoles 230, 231 diamination reactions with TPBT 1,3,5-benztriyne reagent 339 Suzuki’s synthesis of hexaredialene domino aryne nucleophilic-ene cascade 351, 353 339 Suzuki’s synthesis of TCBBs 352 naphthyne from 1,2-benzdiyne-HDDA Suzuki’s synthesis of tetraketone 350 cascade 340 2-benzyl-3-hydroxy-1,4-naphthoquinone process and equivalents 337 126 σ-bond insertion of N–Si and S–Si benzyne 2 bonds 342 cycloisomerization 409–410 3-silylbenzyne 343 dimerization of 31 TPBT with protected thiobenzamides benzyne-ene reaction 470 338, 474 Bergman cyclization 9 1,3-benzdiynes Bettinger’s synthesis, of undecacene 41 equivalents 473 biaryl synthesis 121 Ikawa-Akai’s 343, 344 bicyclohexene 8 Kitamura’s hybrid 344 biphenylene-based starphenes 52, 53 Suzuki’s strategy 343 1,2-bis(trifluoromethylation) 249 1,4-benzdiynes 1, 7 bisanthene 43, 46 actinorhodin 345, 346 bis(pinacolato)diboron onto indolynes bis(sulfonyloxy)diiodobenzene 345, 379 346 bismuthosulfanylation, of arynes 138 1,4-bis(trimethylsilyl)phenyl bis(trimethylsilyl)naphthalenes 43 2,5-bis(triflate) 346, 347 bis-tosylate 472 equivalents 471 boronic esters 192, 325, 329 Ikawa-Akai’s 348, 349 2-bromobenzofuran 362 Kitamura’s hybrid 349 3-bromobenzofuran 2, 361, 363 nanographenes 347, 348 3-bromo-2-chloropyridine 366 vineomcinone B2 methyl ester 350 1-bromocyclohexene 398 benzenediazonium 2-carboxylate 10, 33, 5-bromoindole 369 60, 296, 446 7-bromoindole derivative 371 benzene thiol 133 2-bromophenylboronic ester 192 benzocyclobutene synthesis 122–123 3-bromo-4-(phenylsulfinyl)pyridine 1,3-benzodithiol-2-imine 136 368 490 Index c palladium-catalyzed carbocyclization carbazole-containing alkaloid 201–215 mahanimbine 414 cine-substitution via addition-ring- carbazolyne 384, 414, 469, 478 opening-elimination-ring-closure carboamination, of N-benzoylanilide (ANRORC cine) 361 117 cine-substitution via addition-sub- carbodiimide-derived aza-ortho-quinone stitution-elimination (ASE) 361 methide 163 cine-substitution via trans-halogenation carbodiimides 162, 163 (BCHD) 361 carbolithiation, of arynes 121, 122 (±)-Cis-trikentrin A 384 carbon-carbon triple bond 2, 5, 14, 171, 14C labelling 3 267, 280, 436 cloverphenes 49, 51, 186, 187 carbon nanohorns 61, 62 cobalt-, rhodium- and palladium- carbon nanotubes, by aryne catalyzed corbonylative cycloaddi- cycloadditions 60–61 tion of benzynes 255–260 carbon nucleophiles copper-catalyzed arynes carbanions 452 Ar–Sn bond Addition 244–246 enamines and enolates 453–454 B–B bond addition 244 carboxylic acids 82, 129, 155, 156, 285 1,2-bis(trifluoromethylation) 249–251 catalytic aryne generation methods C–Br bond addition 249 alkynyllithium catalyzed aryne CuCF3 238 generation 326 multi-component reactions Pd-catalyzed aryne generation 324 copper-catalyst 235, 236 Pd-mediated aryne generation from [(IPr)CuCl]-catalyzed synthesis of benzoic acids 324–325 isocoumarins 236–237 Pd-mediated aryne generation from terminal alkynes and activated methyl 2-bromobenzoates 325 alkenes 236 Pd-mediated aryne generation from P–H bond addition 253–255 o-bromoaryl boronic esters 325 sp C–H bond addition 247 C–B, C–I, or C–Cl bond formation, three-component coupling transformations 142 carboamination 230–233 cesium fluoride 126 copper(I) acetylide 232 4-CF3-thiobenzonitrile 242 o-alkynyl aryl iodides 238 C60-graphene hybrids 63 vinylaziridines 232 chelidonine 452, 461, 468, 469 copper-mediated C–H/N–H annulation chiral α-bromoamide 99 reaction 1-chlorocyclohexene 388 of benzamides 224, 225 4-chloroindole derivative 369 of indolobenzamides and arynes 225 2-chloro-3,4-pyridyne 89 cossonidine 457 C–H/N–H annulations coumestans 220, 476 copper 224 C–P bond formation, transformations Ni-catalyzed denitrogenative/ 140–142, 143 annulation 222 crinine 470, 471 palladium-catalyzed arynes 215–222 cryptaustoline 447, 448 Index 491 Curtius-type rearrangement 273, 274, spiroxin C 459 275 trikentrins 462 curvularin 456, 457 vineomycinone B2 methyl ester 472 α-cyanoketones 124 cycloaddition reactions 5 2-cyanophenylstannane 245 [2+2] cycloaddition 393–394 cyclic alkyne 4, 385 cycloalkynes cyclic amines 157, 294, 421 Diels–Alder Reaction 393, 394 cyclic 1,3-dipoles 70, 71, 90–92 1,3-dipoles 394 cyclic ketones 124, 126, 396 [2+2] cycloaddition reactions 15 cycloaddition [3+2] cycloaddition reactions 16 Au(I)-catalyzed benzannulation of 1,2-cycloalkadienes reactions o-alkynyl(oxo)benzenes with [2+2] cycloaddition reaction 401 arynes 198, 201 Diels–Alder reaction 400–401 hetarynes 375–380 1,3-dipolar cycloaddition 401–402 nickel-catalyzed arynes 193 cycloalkynes palladium 184–193 alkenylation reactions 395 of 4,5-pyrimidyne 374 allenic intermediate 386–387 [2+2] cycloaddition 16, 393 14C-labelled l-chlorocyclohexene with aquayamycin 467 phenyllithium 386 of (+)-CC-1065 470 cycloaddition reactions chelidonine 469 [2+2] cycloaddition 393–394 cycloinumakiol 468 Diels–Alder Reaction 393, 394 goupiolone A 468 1,3-dipoles 394 nanaomycin D 466 cycloheptyne 387 ortho-methylbenzaldehydes 468 cyclohexyne 387 polyketides 464 cyclopentyne 387 taxodione 466 dodecahydrotriphenylene from tubingensin B 469 1,2-dibromocyclohexene 385
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