A mechanism study for Pd(II)-catalyzed C(sp 3 )−H activation using a self-cleaving chlorotetrafluoroethylsulfinyl (−SOCF 2 CF 2 Cl) auxiliary as a directing group is reported. Mechanistic studies reveal that (1) the auxiliary group is crucial for C(sp 3 )−H activation, (2) the reaction undergoes a C(sp 3 )−H olefination−Michael addition−removal of the auxiliary sequence, (3) the removal of the auxiliary (SOR f ) is most likely the alcoholic solvolysis of the −SOCF 2 CF 2 Cl group on the N-tri-substituted sulfonamides, and (4) the C(sp 3 )−H cleavage is involved in the rate-determining step.