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

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 [2+2+2] cycloaddition 28 [4+2] cycloadditions fluoride induced cyclohexyne aporphine alkaloids 464 generation aristolactam alkaloids 465 cyclohexenynone 392–393 arizonins B1 459 3,4-oxacyclohexyne 391 arnottin 460 2,3-piperidyne 392 ent-gilvocarcin M 458 3,4-piperidyne 392 ent-Sch 47555 471 insertion reactions 395–396 granaticin A 460 phenyllithium with intramolecular Benzyne-Diene 463 l-chlorocyclohexene 385–386 isocryptolepine 476 reactivity and isolability of 384 isokidamycin 461 traditional methods of ningalins D and G 462 aminotriazoles fragmentation 389 nomitidine 461 base induced 1,2 elimination pseudopterosin aglycon 463 388–389 rifsaliniketal 459 1,2-bishydrazzones oxidation 390 rishirilide B 460 diazirine fragmentation 390 492 Index

cycloalkynes (contd.) 2,3-didehydronaphthalene 34 metal-halogen exchange/elimination Diels–Alder (D–A) reactions 3, 7, 27 389 of tropones 15 vinylidenecarbenes rearrangement diepoxypentacene 36 390, 391 difluorobenzene 471 trapping of 386–387 difunctionalization, of arynes 118, 119, cycloheptyne 386, 387, 388, 389, 390 132, 144, 231, 278–303 cyclohexyne 384, 385, 386, 387, 388, 389, 1,2-difunctionalization of arynes 390, 391, 393, 394, 395, 396, 397, formal insertion of arynes into 400 carbon-carbon bonds cycloinumakiol 467, 468 cyclic ketone 278 cyclopentadienone 20, 29, 42, 43, 58, 1,3-diketones 281 347, 426 β-ketoesters 279, 280 cyclopentyne 385, 386, 387, 389, 390, 391 α-lithiated malonate/an α-lithiated cyclotrimerization nitrile 279 gold-catalyzed self-trimerization of malonates and 1,3-diketones arynes 197, 200 279–280 nickel-catalyzed arynes 193 N-tosylacetimidates/N-tosylacetimid- palladium 184–193 amides 283 α-substituted ketones 281–282 d formal insertion of arynes into dehydrogenation 33, 34, 43, 57, 89, 99, carbon-heteroatom bonds 454 acyl-oxygen and acyl-halogen dehydrohalogenation, of aryl halides 27, σ-bonds 285 316, 318, 368 C–P and C–S bonds 286 3,4-Dehydro-1,5-naphthyridine 362, ethoxyacetylene 287 373, 374 imidazolidines 287 2,3-dehydropyridine-N-oxides 362 imides, ureas, and cyanamides 284 1,2-diallylated benzenes 226 diaroylmethanes 153 secondary amides 283 diaryl sulfoxides or sulfilimines 304 tertiary amides 284, 285 diazo compounds 72, 75 formal insertion of arynes into dibenzophospholederivative, synthesis of heteroatom-heteroatom bonds 122 288 dibenzopyrrocoline alkaloids 447 vicinal formation 289 dibenzosultams 222 1,8-difurylnaphthalene 46 1,2-diborylarene 243 dihalide pyridine precursor 366 1,2-dibromobenzene 141 2,3-dihydro-1H-indazole 298 1,4-dibromobenzene 36 dihydroisoquinolinium N-oxide 86, 87 1,2-dibromocyclohexene 385 9,10-dihydrophenanthrenes 187, 190 dibromoindole 369–370 diiodobenzenes, pyrolysis of 3 dibromoisobenzofuran 35 dimethyl acetylenedicarboxylate (DMAD) 2,3-dibromonaphthalene 34, 35 32, 55, 185, 187, 430 1,3-dicarbonyl compounds 124 1,2-dimethylenecyclobutane 33 1,2-didehydrobenzene diradicals 409 dimethyl maleate 39, 161 Index 493 dinaphthocoronene tetracarboxdiimide DMSO-derived textit-ortho species 171 204 1-dodecanethiol 133 2-diphenyliodonium carboxylate 28 domino aryne generation 19 1,3-diphenylphenanthrofuran 41 domino HDDA 426 1,2-diphosphinobenzene derivatives 141 domino Heck spirocyclization 211, 213 1,3-dipolar cycloaddition 16 double helicene, Synthesis of 55 1,7-dipolar cycloaddition 72 dynemicin A 455, 456 1,3-dipolar cycloaddition reactions 29, 70, 71 e cycloaddition, of arynes 95–97 6π-electrocyclization 478 cycloaddition, with dipoles 92–95 electron-deficient alkynes 32, 153, 154, [3+2] dipolar cycloaddition reactions, 185, 424 cyclic 1,3-dipoles electronic effect arynes, with Münchnones 92 3-borylbenzynes 332 arynes, with sydnones 90–92 3,4-pyridyne 333, 334 [3+2] dipolar cycloaddition reactions, regiocomplementary [3+2] linear 1,3-dipoles cycloaddition 332, 333 arynes with azides 75–79 reversing regioselectivity on arynes, with azomethine imines and 4,5-indolyne 333, 334 ylides 83, 84 silyl groups 331 arynes, with nitrile imines 80 substituted benzynes and hetarynes arynes, with nitrile oxides 79–80 330, 331 arynes, with nitrones 80–83 electron-withdrawing groups 75, 77, arynes, with pyridinium N-imides 159, 207, 229, 301, 305 87–89 elimination-addition (EA) mechanism arynes, with pyridinium N-oxides 360 85–87 elusive bimolecular HDDA reaction arynes, with pyridinium Ylides 433–434 89–90 enal trapping 427 with diazo compounds 72–75 enamines 97, 98, 446, 452, 453–454 formal cycloaddition reactions 97 ent-clavilactone B 453 hydrazone-derived N–N–C systems epoxynaphthalene 14, 27, 35 99–103 2-ethoxybenzofuran 1, 362 N–C–C systems 97, 99, 100 eupolauramine 21, 380, 382, 383 1,3-dipolar cycloadditions (1,3-DC) 70 dipolarophiles 16, 69, 80, 83, 90, 394 f dipolar variant 93 few-layer graphene (FLG) 62 1,3-dipoles 70, 394 final cyclization 46 3,6-di-2-pyridyl-1,2,4,5-tetrazine 35 five-membered hetarynes 7, 359, 361 diselenide 427–428 five-membered heterocycles 70, 80, 361, distal vinylic position 102 365 1,2-disubstituted arenes 150 flash vacuum thermolysis (FVT) 2,4-disubstituted benzothiazole 338 experiment 363 diverse transformations 123 flemichapparin C 220, 476, 477 diynamide 414 fluoride induced cyclohexyne generation 494 Index

cyclohexenynone 392–393 goupiolone A 467–468 3,4-oxacyclohexyne 391 granaticin A 460 2,3-piperidyne 392 Gribble’s bisaryne synthesis, of tetracenes 3,4-piperidyne 392 37 fluoride induced elimination 10 Gribble’s synthesis, of tetracenes 35 azacyclic allene 399 Grob fragmentation 12, 340–341 cycloalkatriene generation 400 guanacastepenes O and N 396, 397 oxacyclic allene 399–400 α-fluoro-β-amino acid derivatives 153 h 3-fluoro-2-iodophenyl triflate 133 halobenzene 2, 9, 316, 319, 324, 336 formal insertion of arynes halogen–metal exchange reactions 446 carbon–carbon bonds 3-halopyridine 365, 367 cyclic ketone 278 Hamura’s synthesis, of substituted β-ketoesters 279, 280 pentacene 36, 39, 53 malonates and 1,3-diketones 279, Hart’s bisaryne synthesis, of 280 dodecamethyltetracene 37 α-substituted ketones 281, 282 Hart’s synthesis, of epoxyacenes 38 carbon–heteroatom bonds Heck-type coupling of benzynes 228 acyl–oxygen and acyl–halogen helical corannulene trimers 57 σ-bonds 285 helicene synthesis 91 C–P and C–S bonds 286 (±)-herbindole A 384 ethoxyacetylene 287 herbindole B 413–414 imidazolidines 287 hetarynes 114 imides, ureas, and cyanamides abnormal addition–elimination (AE ) 284 a mechanism 360, 361 secondary amides 283 addition–elimination (AE ) mechanism tertiary amides 284, 285 n 360 heteroatom–heteroatom bonds cycloaddition reaction 375 C–P and C–S bonds 286 elimination–addition (EA) mechanism N–O bonds 289, 290 organophosphorus acids and 360 sulfinamides 288, 289 five-membered 359, 361 phosphoryl amides 288 indolyne [1,3]-rearrangement 289 herbindole 384 formamide 427–428 lysergic acid synthesis 383 fragmentation, of amino benzotriazoles trikentrin 384 10 insertion reaction 379–380 fredericamycin A 456 nucleophilic addition reactions free radical explanation 2 377–379 fullerobenzyne precursor 60 pyridine ellipticine synthesis 382 g eupolauramine 382, 383 Garg–Houk’s study 328–329 (S)-Macrostomine 382 gold/copper-catalyzed sp C–H bond perlolidine synthesis 381 Addition 247 six membered 359, 361 Index 495 heterocycles 1, 6–7, 21, 30, 70, 80, NHC-borane trapping 427 97, 150, 157, 159, 163–165, 237, nucleophilic trapping agent 432 257, 273, 301, 317–318, 361, 365, 4π-and2π-components 407, 408 369 perylene 426 heterocyclic helicenes 57 [4π+2π] cycloaddition reactions, hetero-Diels–Alder reaction 93 aromatic dienes 416, 417 hexabenzotriphenylene, synthesis of pristine reaction conditions 435 54–55 reaction conditions hexacene 33–34, 39, 426 temperature, pressure, and alkyne hexadehydro Diels–Alder (HDDA) stability 436–437 reaction 1, 11, 114, 149 tolerance for water and oxygen Ag- and B-promoted carbene chemistry 435–436 412–413 substrate concentration 437 aryne formation 315, 428 substrate design 434 aza-HDDA variant 431 trapping agents 433 benzyne cycloisomerization 409, 410 triyne to benzyne 415 classical vs. HDDA benzyne chemistries unanticipated transformation 411 431 hexaphenyltetrabenzopentacene 41 Cu(I)-Catalyzed hydro- and highest occupied molecular orbital halocupration 428 (HOMO) 4–5, 29, 41, 183, 415 de novo arene ring construction 1H-indazoles 72–75 413–414 3H-indazoles 72–74 diselenide 427 Hückel theory 4, 8 diynophile 434 hydrazonyl chlorides 80, 99–100 domino 426 4-hydroxycoumarins 220 elusive bimolecular HDDA reaction 433 i enal 427 ibutamoren mesylate 339, 474 examples of 411–412 Ikawa-Akai’s formamide 427 1,3-benzdiyne strategy 344 half-life measurements 437–438 1,4-benzdiyne strategy 348, 349 intramolecular 424 3-imidopyridinium 94 Lee group 416, 417 3-imidopyridinium species 72, 94 naphthynes via double 424, 425 imine oxides 80 natural products iminoesters 260 colchicine and quinine 420 6,7-indoline 57 phenol 419 indolinyne generation 375 new mechanistic insights 2,3-indolyne 361 dearomatizing ene reaction 424 4,5-indolyne 78 diaziridine 424 2,3-indolyne generation 363 dihydrogen transfer reactions 4,5-indolyne generation 422–423 5-bromoindole 369 silyl ether 424 4-chloroindole derivative 369 thioamides 424 dibromoindole 369–370 three component reactions 421–422 silyltriflate precursor 370 496 Index

5,6-indolyne generation 370 isopropylmagnesium chloride 6,7-indolyne generation (i|i-PrMgCl) 116, 322 7-bromoindole derivative 371–372 isoquinolinium N-oxides 86–87 dichloroindole precursor 371 3,4-Isoquinolyne 373 proton-lithium exchange 371 isotopomers, of phthalic anhydride 3 insertion reactions 17 isoxazolone 392 of arynes 118, 140, 153, 280 insertion reactions, of aryne intermediates j amination and related transformations justicidin B 192, 475 formation of C–N and C–C bonds 116–118 k formation of C–N and C–H bonds Kelly’s synthesis, of molecular ratchet 111–115 48 formation of C–N and C–Mg bonds ketene dithioacetals 102–103 115–116 ketene silyl acetals (KSAs) 123, 321, 340, formation of C–N and C–S, C–P, 343, 350–351, 467, 470, 472 C–Cl, or C–Si bonds 118–121 ketene silyl acetyls (KSAs) 340 bond formation, with nucleophilic β-ketophosphonic acid diester 127 carbons ketoxime-derived nitrones 83 acylalkylations and related Kitamura’s hybrid 1,3-benzdiyne transformations 124–128 equivalent 344 benzocyclobutene synthesis, [2+2] Kitamura’s hybrid 1,4-benzdiyne cycloaddition 122–123 equivalent 349 transformations, carbometalation Kitamura’s synthesis, of substituted 121–122 tetracenes 45 transformations, C–C and C–H bond Kita’s synthesis of fredericamycin A formations 128–129 456 etherification, and transformations Knochel’s aryne precursors 323 129, 132, 133 Kobayashi method 267, 269 in situ generated nitrile oxides 80 Kobayashi’s aryne 183, 391 intramolecular arylation 114 Kobayashi’s fluoride induced aryne intramolecular benzyne–diene [4+2] generation 12–13 cycloaddition 463 Kobayashi’s method 13, 29, 36, 39, 46, intramolecular N-arylation 117 149, 315, 321, 331, 340, 347, 354 iodine-magnesium exchange 114 Kobayashi-typed benzdiyne precursor 2-(2-iodophenoxy)-1-substituted 95 ethanones 204 koenidine 478 1-iodo-2-(2-(phenylethynyl)benzyloxy) benzenes 204 l isobenzofuran 35, 39–40, 52, 290, 386 Larock’s group 201, 215 isochromen-6-ones 204 laserflash photolysis (LFP) 5 α-isocyanoacetamides 152 LiBr elimination 363 β-(2-isocyanophenyloxy)acrylates 290 liphagal 451 isokidamycin 460–461 2-lithio-3-bromo-1-phenylsulfonylindole isolable cyclic 1,3-dipole 90 363 Index 497 lithium di-alkyl(2,2,6,6-tetramethyl- platium-catalyzed boron–boron bond

piperidino)zincate (R2Zn(TMP)Li) addition 243–244 319 sp C–H bond Addition 247 lithium diisopropylamide (LDA) 317, meta-methoxyaniline derivatives 113 319, 320, 336, 372, 459, 463, 470 3-methoxybenzyne 113 lithium 2,2,6,6-tetramethylpiperidide 4-methoxybenzyne 95 (LiTMP) 317–318, 449, 455, 467 4-methylbenzenesulfonate 372 lithium tetramethylpiperidide (LTMP) methyl 2-bromobenzoates 191, 324, 325 38 (trimethylsilyl)methylmagnesium lowest unoccupied molecular orbital chloride 119 (LUMO) 4–6, 13, 29, 111, 183, Michael acceptor 95, 97 434, 445 Michaelis–Arbuzov-type reactions 141 low-valent titanium 41 microporous polymers 48 lysergic acid synthesis 383 molecular gyroscope 48 molecular rearrangements 13–14, 18, m 21, 267–310, 393, 400 (S)-macrostomine 382 molecular rearrangements triggered 1,2-difunctionalization of arynes makaluvamines 369, 380, 384, 448 278–303 m-benzyne 8 four-component reactions with three 2-mercaptobenzothiophenes 103 aryne molecules 308–309 mesogenic tetrabenzopentaphenes 50 monofunctionalization of arynes mesoionic rings 70 nitrogen nucleophiles 268–275 metal bound benzyne 4–5 sulfur nucleophiles 275–278 metal-halogen exchange/elimination 10, three-component reactions with two 326, 389 aryne molecules metallacyclopropenes 5 of 4-hydroxycoumarins 306, 307 metal-metal (or) metal-carbon bond nitriles 306 arynes oximes 306, 308 copper-catalyzed Ar–Sn bond Addition thioureas 306, 307 244–246 1,2,3-trifunctionalization of arynes copper-catalyzed B–B bond addition 303–305 244 3-morpholinobenzyne 114 copper-catalyzed C–Br bond addition Müllen’s synthesis, of pentacene 33 249 multicomponent couplings (MCCs) 14, copper-catalyzed P–H bond addition 18 253–255 reactions of arynes 183, 184 copper-mediated1,2-bis(trifluorom- multicomponent reactions 149 ethylation) 249–251 carbon nucleophile-based gold/copper-catalyzed sp C–H bond multicomponent reactions addition 247–248 active methylenecompounds 153 palladium-catalyzed C–Sn bond isocyanide 150–152 addition 240–241 classification of 150 palladium-catalyzed Sn–Sn/Si–Si bond halogen nucleophile-based 177–179 Addition 241 nitrogen nucleophile-based 498 Index

multicomponent reactions (contd.) benzyne precursors 447 amine 153, 155–159 [2+2] cycloadditions 446, 464–470 diazene 164–165 [4+2] cycloadditions 446, 457–464 imine 159–163 ene reactions 446 N-heteroarene 163–164 nucleophilic additions to benzynes nitrite 165 carbon 452–454 oxygen nucleophile-based nitrogen 447–450 cyclic ether 172–173 oxygen nucleophiles 450–452 dimethylformamide 165–169 transition-metal catalyzed reactions sulfoxide 169–172 474–477 trifluoromethoxide 173–174 N-benzoyloxymorpholine 116 phosphorus nucleophile-based N-benzoylquinolinium imides 93 174–175 N-benzyl-N-tosylenamide 123 sulfur nucleophile-based 176–177 N-boc-2-methyleneglycine derivatives multisubstituted naphthalenes 153 97 Münchnone 70–71, 92 1,n-dipolar cycloaddition 69 1,n-dipoles 69, 70 n Neckers’s synthesis, of hexacene 34

N-alkoxyamides 114 N2 extrusion 35, 39, 43 N-alkoxybenzsulfonamides 222 NHC-borane trapping 427–428 N-alkoxy oxyindoles 99 Ni-catalyzed denitrogenative/annulation N-aminotriazolo-pyridine 366, 368 222–223 nanaomycin D 466 nickel-catalyzed arynes nanographene 50–51, 57, 345, 347, 348, cycloaddition 353 activated alkenes and alkynes 197, 1,2-naphthalyne 91 200 2,6-naphthodiyne synthon 42 with alkynes/eneynes 197 2,3-naphthyne 34 of enynes and arynes 196, 199 naphthynes 6, 34, 36, 40, 49, 340, 3,4-pyridyne with 1,3-diynes 195, 424–426, 428–429 198 N-aryl-2-acylpyrrolidines 273 with unactivated alkenes 196, 199 N-arylation cyclotrimerization of amines 17 with allenes 194, 196 with arynes 126 with diynes 195 of N–H sulfoximine 114 three-component coupling 230 reaction 113 ningalins D and G 462 natural bond orbital (NBO) 76, 78 nitrile imines 16, 70–71, 80, 99, 102, 394 natural product synthesis nitrile oxides 16, 70, 77–80, 394, 401 addition–fragmentation reaction nitrogen nucleophiles 454––457 acronycine 450 1,3-benzdiyne equivalents 473 aryne-triggered Sommelet–Hauser 1,4-benzdiyne equivalents 471 rearrangement of tertiary benzylic benzyne–ene reaction 470–471 amines 269, 271 benzyne generation via hexadehydro- aryne-triggered [2,3]-Stevens Diels–Alder reaction 477–479 rearrangement 273 Index 499

benzye-induced [1,4]-rearrangement nucleophilic organophosphorus 270, 271 compounds 140 cryptaustoline 448 nucleophilic organosulfur compounds Curtius-type rearrangement 273, 275 133 dibenzopyrrocoline alkaloids 447 nucleophilic substitution reaction 2, 360 dictyodendrin A 449 N-vinyl-α,β-unsaturated nitrones 81 textit-benzyl glycinate 270 of hinckdentine A 450 o indolactam V 450 O allyl migration 172 isobatzelline C 448 o-aminoarylsilanes 119 makaluvamine A 448 O-arylation, with arynes 82 quinazolinone alkaloids 450 o-benzoxazolylhydroxylamines 230 (aminomethyl)silane 268 o-benzyne 4 three-component reaction of pyridines, o-dihaloaryls 27 arynes and isatins 275 o-haloaryl sulfonates 321 triethylamine 268 o-iodoaryl sulfonates 116 nitrones 16, 70–71, 78, 80–83, 85, 87, o-iodoaryl triflates 114, 123, 321 308, 331, 376, 394, 401–402 one-pot transformation 35, 39 N-methoxybenzamides 217, 219 one-pot tricyclic phenanthridinones N-methylcrinasiadine 476 217 N-methyltetrahydroquinoline 157 organolithium reagents 179–180 N-monosubstituted hydrazones 101 organometallic reagents 10, 225, 227 N-monosubstituted hydrazonyl chlorides organonitrogen compounds 114, 116 99 organophophorus compounds 140–142 N,N-dialkylanilines 157 ortho-formyl diaryl ethers 169 N,N-dimethylaniline 114 ortho-methylbenzaldehydes 468 N,N-dimethylhydrazone 118 ortho-olefinated biphenyls 190 N,N-dimethylhydrazonyl chlorides 100 ortho-quinoid species 170 nomitidine 461 ortho-quinone methide 168, 169 non-anionic nucleophiles 445 1,3,8-nonatriyne 409 ortho-silyl aryltriflates 183 non-zwitterionic amphiphiles 70 ortho-(trifluoromethoxy)aryl anion 173 N—O single bond 85 ortho-(trimethylsilyl)phenyl triflate 183 N-substituted-N-(2-halophenyl) o-silylaryltriflates 50, 111, 119, 133 formamides 209 o-silylaryl triflate-type 3-sulfanylaryne N-substituted phenanthridinones 209 precursors 138 N-tosylhydrazones 75, 101 o-siylphenyl triflate 321 N-tosylisoquinolinium imides 89 o-transpositioned ketones 93 N-(trifluoroacetyl)anilides 118 o-(trimethylsilyl)phenyl triflate 28 Nuckolls’s synthesis, of substituted oxacyclic allene 399–400 pentacenes 45 3,4-oxacyclohexyne 387, 391 nucleophilic addition reactions 332, 370, oxidative photocyclization reactions 55 375, 378–379, 402 3-oxidopyridinium dipole 72 hetarynes 377 oxonium Claisen rearrangement 172, nucleophilic C–C bond formation 122 304, 351 500 Index

oxygen nucleophiles 165–174, 284, 446, cloverphene 187 450–452 coupling of alkenes 190 oxysulfanylations, of aryne intermediates substituted indole based arynes 192 132, 135 Pd(0) oxidation state 184 Sn–Sn/Si–Si bond addition 241 p three-component coupling paddle-wheel nanostructures 59–60 with allylic epoxides and terminal palladacycloheptadiene 190 alkynes 228 palladium-catalyzed arynes allylic halides and alkynyl stannanes ArS–CN addition 241–243 226 co-cyclization 185 arynes, isocyanides and C–Sn bond addition 240–241 cyanoformates 230, 231 ctrimerization of (2-bromophenyl) arynes, terminal alkynes, and vinyl boronic esters 192 cyclopropanedicarboxylate 229, in C–X annulations 230 aryl ketone O-acetyloximes 215, 217 bis-allylation 226 benzophenone O-perfluorobenzoyl Heck-type coupling 228, 229 oximes 215 Sonogashira type coupling 227 dibenzosultams 222 Stille and Suzuki coupling reactions N-acylcarbazoles 215, 216 227 N-methoxybenzamides 217, 219 three-component reaction N-methyl benzylamines 221 carbon monoxide and 2-iodoanilines one-pot tricyclic phenanthridinones 259 217, 219 palladium-catalyzed carbocyclization ortho-halobenzamides 216 aromatic halides with arynes 202, 203 phenanthridinones 221 arynes with allyl-substituted phthalimides 222, 223 iodocyclohexenones and quinolinones 218, 220 iodofuranones 209 cycloaddition with alkynes 186 arynes with propargylic carbonates allylic chlorides or alkynes 188 207 benzodiynes 188 biscarbocyclization reactions 206 benzoic acids 191, 192 carbopalladation of arynes with cloverphene 186, 187 iodo-aryl-alkenes 213, 214 conjugated dienes 192 chemoselective [3+2] spiroannulation indole-based conjugated trimers of 2-halobiaryls with arynes 216 192 (diarylmethylene)cyclopropa[b]- methyl 2-bromobenzoates 191 naphthalenes with arynes 206 substituted diynes 188, 189 dinaphthocoronene tetracarboxdiimide cyclocarbonylation 204 1H-inden-1-ones 259 domino Heck spirocyclization 211, cyclotrimerization 185 212 allenes 190 2-halobiaryls with arynes 201, 202 bicyclic alkene 187, 188 indolo-[1,2-f ]phenanthridines 203 carbon-carbon π-components 185 2-iodobenzyl-3-phenylpropiolates 204 Index 501

2-(2-iodophenoxy)-1-substituted π-extended starphenes, synthesis of ethanones 204 49–52, 54 N-(2-halophenyl)formamides with 3,4-phenanthryne 91 arynes 210 phenyl(2-(trimethylsilyl) phenyl) N-(2-phenylallyl)sulphonamides with iodonium triflate 10–11 arynes 210, 212 phenylpropiolic acid 408 o-halobenzaldehydes with arynes 203 phenylsulfanylation, of arynes 135 ortho-halostryrenes with arynes 210, 1-phenylsulfonyl-2,3-indolyne 363 211 3-(phenylthio)benzyne 114 polycyclic dibenzocoronene (2-aminoaryl)phosphine oxides 288 bis(dicarboximide) 204 α-phosphinylacetonitrile 127 substituted o-halostyrenes with arynes photoinduced aryne generation methods 208 323 three-component coupling of aromatic photoinitiated benzenediazonium halides with alkynes and arynes carboxylates decomposition 3 202, 204 platinum-catalyzed boron-boron bond three component coupling of aromatic addition 243–244 iodides with P–Li bonds 140 bicyclic/heterobicyclic alkenes and polycyclic aromatic compounds 19–20, arynes 203, 205 54, 185, 188, 201, 345 palladium-catalyzed [2+2+2] polycyclic aromatic hydrocarbons (PAHs) cocyclotrimerization 32, 49 19–20, 29–31, 48–55, 57–58, 204, palladium-catalyzed cocyclotrimerization, 345–346, 353–354, 393–394 of arynes 49 polycyclic aryne precursors 187 palladium-catalyzed cyclotrimerization, polycyclic dibenzocoronene of indolynes 57 bis(dicarboximide) 204 papaverine 238, 453 porous triptycene-based molecules 48 Pascal’s synthesis, of twisted substituted possible reactivity modes of pentacene 42 arylation reactions 17 p-benzyne intermediates 8 insertion reactions 17 Pd-catalyzed aryne generation 324, 325 MCC 18, 19 Pd-mediated aryne generation molecular rearrangements 18–19 from benzoic acids 325 pericyclic reactions 14–16 from methyl 2-bromobenzoates 325 transition metal-catalyzed reactions from o-bromoaryl boronic esters 325 18 Peña’s synthesis, of decacene 40 prefluoroalkoxylation–bromination pentahelicene 56 reactions 174 1,3-pentanedione 126 proton-lithium exchange 371 Pérez–Peña synthesis, of benzo-fused pseudopterosin aglycon 463 substituted acenes 44 pyrazolo[5,1-a]isoquinolines 239–240 Pérez’s synthesis 58 2,3-pyridine dicarboxylic anhydride 7 pericyclic reactions 13–15, 315, 339, 446 pyridinium N-oxides 71, 85–87, 96 perlolidine 380–381 1,2-pyridyne 362 perylene 43, 45–47, 426 2,3-pyridyne 377 perylenebisimides (PBIs) 46, 47 dihalide pyridine precursor 366 502 Index

2,3-pyridyne (contd.) rishirilide B 459–460 3-halopyridine 365–366 Ritter-type reactions 416 N-aminotriazolo-pyridine 366 3-(trimethylsilyl)pyridin-2-yl s trifluoromethanesulfonate 367 scanning tunnelling microscopy (STM) pyridyne-N-oxides generation 40, 50, 53 374–375 Schlüter’s synthesis, of epoxyacenes 38 3,4-pyridynes 7, 378, 380 selaginpulvilin C 414, 478 3-bromo-4-(phenylsulfinyl)pyridine selaginpulvin C 413–414 368 1,3-sigmatropic-like rearrangement 86 3-halopyridine 367–368 1,3-sigmatropic rearrangement 83 N-aminotriazolo-pyridine 368 silver-catalyzed [3+2] cycloaddition of thermolysis of diazonium carboxylates arynes 74, 260–261 367 silylamination, of arynes 119, 121, 141 4-trialkylsilyl-3-pyridyl triflate 368, silylaryl triflates 70, 114, 119, 138, 267, 369 269–270, 272–273, 275–276, 4,5-pyrimidyne 77, 373 279–281, 283, 285–290, 292, α-pyrones 462 294–295, 298–299, 301, 303–306, pyrroloindole 474 309, 321, 345, 449, 451, 453–454, 3,4-pyrrolynes 364 456–457, 460–461, 464, 468, 474–477 q 3-silylbenzyne 77 quinolynes generation silyl ether 351, 411, 423–424, 428, 463 5,6- and 7,8-dehydroquinolines 372 silylmethyl Grignard reagent 114, 121, 3,4-isoquinolyne 373 133, 322 7,8-quinolyne 372, 373 silylphosphination, of arynes 141, 143 3,4-quinolyne from halo derivatives silyl-protected carboxylic acids 285 372 silyltriflate precursor 370, 372, 378, 391, 393 r singlet-triplet splitting 3, 8 regioselective amination, of pyridynes six membered hetarynes 7, 359, 361 114 small ring-fused arynes 335–336 regioselectivity Sommelet–Hauser rearrangement in aryne reactions 3 269–271 rationales 78 Sonogashira type coupling 227–228 of unsymmetrical benzyne 77 sp2-hybridization 70 resonance stabilization energies (RSE) spiropalladacycle 212 415, 434 spiroxin C 459 retro-D–A reaction 33, 35, 37–39 S-silyl sulfides 136 retrojusticidin B 192, 475 starphenes 48–54 retro-6π electrocyclization 94 steric effect Rickborn’s synthesis 3-alkyl groups on arynes 327, 328 of pentacene 37 boronic esters 329 of tetracene 35 Garg–Houk’s study 329 rifsaliniketal 458–459 silyl 328 Index 503

trimethylsilyl (TMS) group 328 Suzuki’s synthesis of TCBBs 352 [1,2]-Stevens rearrangement 268 Suzuki’s synthesis of tetraketone 350 strained cyclic allenes sydnone 70–71, 78, 90–92 1,2-cycloalkadienes generation symmetrical tetraynes 412, 424, 426, 432 base induced 1,6-elimination 397 cyclopropylidenes rearrangement t 398 taiwanins 188–189, 475 fluoride induced elimination tandem aryne cycloadditions 47 398–400 tandem [4+2]/[2+2] cycloaddition 16 via pyrolysis of ketene 398 tandem HDDA/TDDA 426 1,2-cycloalkadienes reactions 400 taxodione 466 styrenes, reaction of 15 terminal alkynes 18, 75, 113, 162, α-substituted α-diazophosphonate 74 227–232, 235–239, 247–248, 251, sulfanylation 253, 437, 469 hydrosulfanylation, of arynes 133, 135 α-(tert-butoxycarbonylamino)acrylic acid transformations, C–S and C–C bond methyl ester 118 formations 135 tert-butyldimethylsilyl (TBDMS) group transformations, C–S and C–X bond 329 formations 136, 138, 140 tert-butylisocyanide 159 sulfanylation reactions, of arynes 133 tetrabenzoheptaphenes 187 sulfanyl magnesiations, of arynes 136 tetrabenzopentaphenes 49–50 sulfur 102–103, 170, 176–177, 275–278, 1,2,4,5-tetrabromobenzene 40 299, 302–304, 306, 363, 426, 434 tetrabutylammonium sulfur nucleophiles difluorotriphenylsilicate (TBAT) aryne-triggered [1,2]-Stevens 13, 141, 283, 454 rearrangement 275 tetrabutyl ammonium fluoride (TBAF) aryne-triggered [1,2]-Stevens 13, 42–43, 50, 59, 62, 79–80, 85, rearrangement of benzylic 126, 155, 271, 458 thioethers 276 tetrabutyl ammonium iodide (TBAI) aryne-trigger [2,3]-Stevens rearrangement of allylic thioethers 172–173, 224 276, 277 tetrabutylammonium aryne-trigger [2,3]-Stevens triphenyldifluorosilicate (TBAT) rearrangement of propargylic 13, 141, 283–284, 454 thioethers 276, 277 tetracenes 33–35, 39, 43, 45 benzyne-triggered [2,3]-Stevens tetracenomycins C and X 472, 473 rearrangement of allylic thioethers tetrachlorothiophenedioxide 33 276, 277 tetradehydrobenzenes 7 superior electrophile 183 tetradehydro-Diels–Alder (TDDA) Suzuki–Miyaura C–C coupling 46 reaction 408–409, 411, 426, 435 Suzuki–Miyaura cross-coupling reactions tetraepoxydecacene 39–40 243, 379 tetrahydrofuran (THF) 13, 85, 135, 163, Suzuki’s 1,3-benzdiyne strategy 343 172–173, 241, 345, 409, 422, 435, Suzuki’s synthesis of hexaredialene 351, 455, 458, 465, 467 353 tetrahydroisoquinoline skeleton 470 504 Index

tetrahydro naphthalenes via Diels–Alder triflyloxy (OTf) group 319 reaction 394 triflyloxy (OTf)-substituted 1,2,3,6-tetrahydropyridine-2-carboxylate benzocyclobutenones 179, 180 273 1,2,3-trifunctionalization, of aromatic ring 1,2,4,5-tetraiodobenzene 194 172 β-tetralone 124 1,2,3-trifunctionalization of arynes 303 2,2,6,6-tetramethyl-1-piperidinyloxy trikentrins 462 (TEMPO) 40 trimerization 2 tetramethylpyrrole 36 2-(trimethylsilyl)aryl triflates 12, 149 tetra-n-butylammonium fluoride 183 trimethylsilyl (TMS) group 173, tetraphenylcyclopentadienone (TPCPD) 319–322, 328, 337, 339, 344–345, 29, 37, 366, 393, 424, 425 348 tetraphenyltetrabenzoheptacene 41, 42 2-(trimethylsilyl)-1,3-phenylene thiacycloalkyne 387 bis(trifluoromethanesulfonate) thianaphthene-2,3-dicarboxylic acid (TPBT) 1, 337 anhydride 363 3-(trimethylsilyl)pyridin-2-yl thianthrene 136 trifluoromethanesulfonate 367 3,4-thiophyne 364 triphenylene 2, 12, 31, 52, 185, 191–192, thioxantone synthesis 133 197, 202, 324 Thummel’s synthesis 33 triphenylphosphine 114, 118, 159, 303 tosylhydrazine 164, 165, 239–240 triple bond 2–5, 36, 69, 77, 171–172, 180, toxyloxanthone B 451 267, 280, 286, 321, 330, 333, 370, transition metal-catalyzed reactions 18, 384, 424, 431, 436, 446 149, 183–261, 315, 354, 474–477 triptycene sensors, for explosives 49 transition metal catalyzed triscoranylene, synthesis of 57 three-component coupling reactions triyne precursors 445, 477 copper 230–239 tubingensin A 381, 384, 454–455 Ni-catalyzed arynes 230 tubingensin B 381, 384, 469 palladium-catalyzed arynes 225–230 turkiyenine 456–457 silver 239–2407 tylophorine 210, 476, 477 4-trialkylsilyl-3-pyridyl triflate 368, 369 tricarbonyl compound 126 u tricyclobutabenzene (TCBB) 350–352 Uchiyama’s conditions 319 tridehydrobenzenes 7 ultra-high vacuum (UHV) 27, 39–40, 53 triepoxypentacene 39 urea insertion onto hetarynes 379 triflones 303–304 UV spectra 3 trifluoroacetic acid (TFA) 36, 155–156 2-(trifluoroacetylamino)pyridine 114 v trifluoromethoxide anion 173 vicinal carbon trifluoromethoxylation–bromination carbon/carbon–carbon bond-forming products 173 reactions of arynes 289–292 3-(triflyloxy)aryne intermediate 119 carbon/carbon–heteroatom 3-triflyloxy arynes 12, 136 bond-forming reactions of arynes 3-triflyloxybenzyne 114, 303 acyl hydrazides 298, 299 Index 505

1-aroyl-3,4-dihydroisoquinolines vinylogous quinolinium imides 93 299, 300 vinyl sulfoxides 302–303 aryl sulfonamides 299, 300 1-vinyl-1,2,3,4-tetrahydroisoquinolines aryne-triggered aza-Claisen 273 rearrangement of tertiary allylic vitamine E core 452 amines 293, 294 aryne-triggered propargyl Claisen w rearrangement 294, 295 welwitindolinone alkaloid 454–455 diazo compounds 296, 297 Woodward–Hoffmann rules 30–31, 122 N-hydroxyindoles 295 Wudl’s synthesis nitrosoarenes 296 of benzo-fused substituted heptacene pyridine N-oxides 298 43 thioamides 296, 297 of heptacene 38 three-component reaction of arynes, Wurtz reaction 2 tertiary aromatic amines, and carbon dioxide 301, 302 x three-component reaction of arynes, X-ray crystallography 4, 212, 222, 363 tertiary aromatic amines, and xylopinine 453 carbonyl compounds 301 heteroatom/carbon–heteroatom z bond-forming reactions of arynes Zhang’s synthesis, of dodecatwistacene 302 42 vineomycinone B2 methyl ester zwitterionic 2, 10, 70, 103, 136, 162, 348–350, 472 267–268, 303, 421, 454