Mechanism and Synthetic Applications of the Photochemical Generation and X-H Insertion Reactions of Oxacarbenes

Article abstract of DOI:10.1021/ja00197a049

A kinetic study of the photochemical ring expansion of cyclobutanones to oxacarbenes has shown that, in the presence of alcohol, the oxacarbene is generated irreversibly.Substrates for the intramolecular versions of the oxacarbene generation-insertion sequence (heteroalkylcyclobutanones) were prepared by an intramolecular <2 + 2>-Baeyer-Villiger sequence.These have been used to form 5-, 6-, 7-, and 8-membered nitrogen, oxygen, and sulfur bicyclic ring systems.