Palladium-catalyzed Insertion Reactions of Isocyanides into Thiocarbamates and Selenocarbamates

The insertion reaction of isocyanides with thiocarbamates and selenocarbamates in the presence of a Pd(0) catalyst to selectively give 2-oxoethanimidothioates and -selenoates is reported. This is the first example of the insertion of an isocyanide into a carbon heteroatom bond using a transition-metal catalyst. DFT calculations suggest that the reaction proceeds through a thiopalladation pathway at the migratory insertion process.