Cleavage and Reassembly of the C═O Bond of 2-Alkynylbenzaldehydes: A Metal-Free Access to Inden-1-ones.

A metal-free approach to inden-1-ones from 2-alkynylbenzaldehydes mediated by pyrrolidine has been developed. The reaction proceeds under mild conditions in a step- and atom-economy process by cleaving the C═O bond and constructing new C-C as well as C═O bonds. Oxygen-18 and deuterium labeling experiments revealed an aza-Petasis-Ferrier rearrangement of an intermediate 1-amino-3-methylene-dihydroisobenzofuran.