Azepine cycloaddition reactions

IH-Azepine, 1-methoxy carbonyl-cycloaddition reactions, 7, 522 with nitrosobenzene, 7, 520 tricarbonyliron complex acylation, 7, 512-513 conformation, 7, 494 tricarbonylruthenium complex cycloaddition reactions, 7, 520 1 H-Azepine, l-methoxycarbonyl-6,7-dihydro-synthesis, 7, 507... 

H-Azepine, 2-methyl-1-methoxycarbonyl-rearrangement, 7, 504 1 //-Azepine, 3-methyl-1 -methoxycarbonyl-cycloaddition reactions, 7, 520 IH-Azepine, 1-phenyl-synthesis, 7, 542 1 H-Azepine, N-phthalimido-formation, 7, 508 IH-Azepine, N-sulfonyl-UV spectra, 7, 501 1 H-Azepine, tetrahydromethylene-synthesis, 7, 540 IH-Azepine, N-p-tosyl-protonation, 7, 509 synthesis, 7, 537 3H-Azepine, 3-acyl-2-alkoxy-synthesis, 7, 542-543 3H-Azepine, 3-acyl-2-methoxy-rearrangements, 7, 505 3H-Azepine, 2-alkoxy-hydrolysis, 7, 510... 

Schmidt reaction of ketones, 7, 530 from thienylnitrenes, 4, 820 tautomers, 7, 492 thermal reactions, 7, 503 transition metal complexes reactivity, 7, 28 tungsten complexes, 7, 523 UV spectra, 7, 501 X-ray analysis, 7, 494 1 H-Azepines conformation, 7, 492 cycloaddition reactions, 7, 520, 522 dimerization, 7, 508 H NMR, 7, 495 isomerization, 7, 519 metal complexes, 7, 512 photoaddition reactions with oxygen, 7, 523 protonation, 7, 509 ring contractions, 7, 506 sigmatropic rearrangements, 7, 506 stability, 7, 492 N-substituted mass spectra, 7, 501 rearrangements, 7, 504 synthesis, 7, 536-537... 

With the exception of the photosensitized reaction of methyl acrylate with 1-benzoylindole to produce the four-membered ring adduct, with subsequent conversion into a benz[6]azepine, no other photoinduced cycloaddition reactions of indoles with alkenes have been reported (80 3403). 

Azepine, 1-ethoxycarbonyl-cycloaddition reactions, 7, 520, 521 electrophilic reactions, 7, 524 protonation, 7, 509 reactions... 

Scheme 47 Photolytic cycloaddition reaction of azepines with Cgo-...

The novel pyrazolo[l,5-a]azepine (84) is prepared by the cycloaddition reaction of 3a,6a-diazepentalene (83) with dimethyl acetylenedicarboxylate <95JCR(S)338>. 

The oxirane fused azepine 40, formed by an intramolecular [5+2] cycloaddition reaction undergoes an acid promoted rearrangement to yield the tricyclic derivative 41. The structure was confirmed by X-ray crystallography of the nitrobenzoate ester <07OL4681>. 

Dibenzazepines and other tricyclic azepines, general review 84HC(43,1)1. Heteroazepines, cyclization and cycloaddition reactions of 81H(15)1569. 5//-Isoindolo[l,2-h 3]benzazepines, synthesis and biological activity of ... 

The A-pentenyl-substituted maleimide 40 undergoes an efficient formal [5 + 2] cycloaddition reaction upon UV irradiation and forms azepine 42. The reaction was thought to proceed by initial [2 -+- 2] cycloaddition to form zwit-terion 41, which evolved to 42 via a fragmentation step (Scheme 2.23). This... 

A useful reaction for the synthesis of unsaturated seven-membered heterocycles is the (2 + 2)-cycloaddition of heteroaromatic compounds, e.g., 1 //-pyrrole, furan, or thiophene derivatives, with acetylenes. In combination with a subsequent intramolecular (2 + 2)-cycloreversion (Section IV,B,2) of the annulated cyclobutene moiety, ring enlargement with two carbon atoms can be achieved. 1-Heterocycloheptatrienes, such as benzol6]azepines,26,27,65,66 benzo[fc]oxepins,67,68 benzo[6]-thiepins,69,70 and thiepins,18,71 have been successfully prepared in this way other routes are either nonexistent or laborious.72 In these compounds the reacting carbon-carbon double bond constitutes part of a (4n + 2)7r-electron system and in the (2 + 2)-cycloaddition the resonance energy of the aromatic nucleus is lost. Just like the nonaromatic heterocycles, heteroaromatic compounds have been reported to undergo (2 + 2)-cycloaddition reactions both with electron-deficient and with electron-rich acetylenes. 

It should be pointed out that the formation of azepine in reaction with ethylazi-doformate was observed only in case of hexafluorobenzene and the same reaction of fluorinated naphtalenes led to the exclusive formation of the corresponding aziridines as the result of [1 + 2] cycloaddition of the EtOC(0)N to fluorinated C=C of naphthalene." Azepines 60-62 undergo clean, high-yield photochemical isomerization with formation of the corresponding hexafluoro-2-azabicyclo[3.2.0] hepta-3,6-dienes." ... 

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