Expedient Synthesis of Fused Azepine Derivatives using a Sequential Rh(II)-Catalyzed Cyclopropanation/1-Aza-Cope Rearrangement of Dienyltriazoles

摘要

A general method for the formation of fused dihydroazepine derivatives from 1-sulfonyl-1,2,3-triazoles bearing a tethered diene is reported. The process involves an intramolecular cyclopropanation of an α-imino Rh(II)-carbenoid, leading to a transient 1-imino-2-vinylcyclopropane intermediate which rapidly undergoes a 1-aza-Cope rearrangement to generate fused dihydroazepine derivatives in moderate to excellent yields. The reaction proceeds with similar efficiency on gram-scale. The use of catalyst-free conditions leads to the formation of a novel [4.4.0] bicyclic heterocycle.