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

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.

Automated summary

Novel annulations have been developed via ketene intermediates using allenyl imide and alkynoates with good leaving groups 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 yield 1,3-thiazin-4-ones and 5-alkenyl thiazolones in high yields, respectively, with proposed reaction mechanisms based on deuterium labeling experiments and density functional theory calculations.