An unprecedented rearrangement/anellation sequence allows the clean synthesis of azepino[3,4‐b]indol‐1‐ones from readily available starting materials. Alkyne‐substituted indole‐3‐carboxamides were prepared and converted to azepino[3,4‐b]indol‐1‐ones by the SPhosAuNTf₂ catalyst (SPhos=2‐dicyclohexylphosphino‐2′,6′‐dimethoxybiphenyl). The new connectivity, which involves an unprecedented 3,2‐shift of an acylamino group for the product formation, was proven by a crystal structure analysis.

中文翻译：

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金催化：炔烃取代的吲哚-3-羧酰胺中的高效和区域选择性羰基迁移，导致阿斯皮诺[3,4-b]吲哚-1-酮

前所未有的重排/修饰顺序，可以从容易获得的起始原料中干净合成azepino [3,4- b ]吲哚-1-酮。制备了炔基取代的吲哚-3-羧酰胺，并通过SPhosAuNTf ₂催化剂（SPhos = 2-二环己基膦基磷酸2'，6'-二甲氧基联苯）转化为azepino [3,4- b ]吲哚-1-酮。晶体结构分析证明了这种新的连接性，其中涉及到空前的酰氨基3,2位移位以形成产物。