π-Stacking-Controlled Dearomatic Sulfur-Shifted Ene Reaction of Ketenes and Polycyclic Arylthiiranes: Access to Areno[ d]-ε-thiolactones

J Org Chem. 2024 Apr 5;89(7):4749-4759. doi: 10.1021/acs.joc.3c02990. Epub 2024 Mar 19.

Abstract

Electrophilic ring-expansion of polycyclic arylthiiranes and ketenes generated from alkoxy/aryloxyacetyl chlorides in the presence of triethylamine (TEA) is developed and provides a new strategy for the synthesis of areno[d]-ε-thiolactones, areno[d]thiepinones, directly without catalysts or additives. This strategy features atom- and step-economic one-pot characteristic via a tandem sequence of in situ ketene generation, π-stacking-controlled dearomatic sulfur-shifted ene, and aromatization. The current reaction is a novel strategy of electrophilic ring expansions of three-membered saturated heterocycles.