Highly Selective and Catalytic C–N Bond Cleavage of Tertiary Sulfonamides: Scope and Mechanistic Insight

[Image: see text] A highly chemoselective C–N bond cleavage reaction of p-methoxybenzyl- (PMB), 3,4-dimethoxybenzyl- (DMB), or cinnamyl-substituted tertiary sulfonamides in the presence of catalytic Bi(OTf)(3) is presented. A wide range of sulfonamide substrates smoothly furnished the corresponding C–N bond cleavage products in good to excellent yields. Great efforts have been made to obtain insights into the reaction mechanism based on a series of control experiments and mass spectroscopy.