Transformation of Zwitterionic Pyridine Derivatives to a Spiro-Fused Ring System: Azoniabenzo[de]fluorine. Synthesis and Mechanistic Rationalization

J Org Chem. 2015 Jan 2;80(1):174-9. doi: 10.1021/jo5022663. Epub 2014 Dec 5.

Abstract

Reaction of aryl- and benzylsulfanopyridinium amidates bearing a methyl group in position 6 with 2 equiv of diphenylketene afforded a spiro-fused ring system: azoniabenzo[de]fluorine. By use of an excess amount of ketene, a distinct reaction was observed via which a 1H-pyrrolo[3,2-b]pyridin-2(3H)-one derivative was furnished. The structure of the tetracyclic spiro-fused ring system was unambiguously confirmed by X-ray diffraction, and its formation was rationalized by DFT calculations.