A novel and efficient method for the Cr(II)-mediated desulfonylation of 伪-sulfonyl ketone by a Cr鈥搇igand鈥揗n system has been developed during the course of process research on Halaven (eribulin mesylate). This reaction is dramatically accelerated in the presence of an appropriate bipyridyl-type ligand. This system is applicable to reduction of 伪-sulfur-substituted ketones. In addition, a Cr鈥揅p2ZrCl2鈥揗n catalytic system is also applicable to desulfonylation of 伪-sulfonyl ketone.