Palladium-Catalyzed Azathiolation of Carbon Monoxide

A novel palladium-catalyzed azathiolation of carbon monoxide using sulfenamide (RSNR‘2) (1) is described to provide thiocarbamate 2 in good yields. The mechanistic proposal includes the following:  (1) insertion of CO into Pd−S bond of Pd(SR)2(PPh3)n 4 to provide Pd[C(O)SR](SR)(PPh3)n 5 and (2) σ-bond metathesis between S−N and Pd−C(O) bonds to afford 2 with the regeneration of 4.