Decomposition of Alkynyl Hydrazones: Synthesis of Allenoates, Dihaloallenoates, and Angularly Fused Tricyclic Azepines.

An unprecedented decomposition of unprotected alkynyl hydrazones is attempted that has provided allenoates, tetrasubstituted α,γ-dihaloallenoates, and functionalized tricyclic azepines. A reaction of alkynyl hydrazones with N -halosuccinimides captures the electrophile in 2-fold that delivers fully substituted dibromo- and diiodoallenoates in good yields. In addition, a DABCO-promoted Wolff-Kishner reduction of hydrazones, followed by isomerization, provides versatile allenoates under mild conditions. In contrast, a similar decomposition with ambiphilic DBU furnishes a completely different tricyclic azepine scaffold in excellent yield and diastereoselectivity.