Esterification of Thioamides via Selective N-C(S) Cleavage under Mild Conditions

Herein, we report an exceedingly mild method for thedirect, transition-metal-freeesterification of thioamides through the selective generation of tetrahedralintermediates. The method represents the first transition-metal-freeapproach to the thioamide to thionoester transformation in organicsynthesis. This reactivity has been accomplished through N,N-Boc(2)-thioamides that engage in ground-state destabilizationof the n(N) & RARR; & pi;*(C S) conjugation.The ground-state destabilization of single-atom bioisostericthioamides will expand the arsenal of valuable amide bond functionalizationreactions.

Automated summary

This study reports an extremely mild method for the direct, transition-metal-free esterification of thioamides through the selective generation of tetrahedral intermediates. It represents the first transition-metal-free approach to the thioamide to thionoester transformation in organic synthesis. The ground-state destabilization of single-atom bioisosteric thioamides will expand the arsenal of valuable amide bond functionalization reactions.