Phosphine-Catalyzed Annulations Based on [3+3] and [3+2] Trapping of Ketene Intermediates with Thioamides

Org Lett. 2021 Nov 5;23(21):8147-8152. doi: 10.1021/acs.orglett.1c02803. Epub 2021 Oct 18.

Abstract

With the aim of developing novel annulations via ketene intermediates, allenyl imide and alkynoates bearing good leaving groups are used for their function in a tandem conjugate addition-elimination reaction (SN2' type) promoted by nucleophilic phosphine catalysts. By utilizing thioamides as 1S,3N-bis-nucleophiles, [3+3] and [3+2] annulations have been established to allow rapid access to 1,3-thiazin-4-ones and 5-alkenyl thiazolones in high yields, respectively. Furthermore, the possible reaction mechanisms are proposed on the basis of deuterium labeling experiments and density functional theory calculations.

Publication types

  • Research Support, Non-U.S. Gov't