Chloroform as a Carbon Monoxide Precursor: In or Ex Situ Generation of CO for Pd-Catalyzed Aminocarbonylations

Conditions for the rapid hydrolysis of chloroform to carbon monoxide (CO) using heterogeneous CsOH center dot H2O am described. CO and (CO)-C-13 can be generated cleanly and rapidly under mild conditions and can be captured either in or ex situ in palladium-catalyzed aminocarbonylation reactions. Utilizing only 1-3 equiv of CO allows for the aminocarbonylation of aryl, vinyl, and benzyl halide with a wide variety of primary and secondary amines giving amide products in good to excellent yields.