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Great efforts have been made in the activation of a C(alkenyl)-H bond vicinal to the directing group to proceed  via  five- or six-membered  endo -metallocycles. In stark contrast, functionalization of a C(alkenyl)-H bond geminal to the directing group via  exo -metallocycle pathway continued to be elusive. Here we report the selective transformation of an olefinic C-H bond that is geminal to the directing group bearing valuable hydroxyl, carbamate or amide into a C-C bond, which proceeds through four- to eight-membered  exo -palladacycles. Compared to the reported mechanisms proceeding only through six-membered  exo -palladacycles via  N,N -bidentate chelation, our weak and  O -monodentate chelation-assisted C(alkenyl)-H activations tolerate longer or shorter distances between the olefinic C-H bonds and the coordinating groups, allowing for the functionalizations of many olefinic C-H bonds in alkenyl alcohols, carbamates and amides. The synthetic applicability has been demonstrated by the preparative scale and late-stage C-H functionalization of steroid and ricinoleate derivatives.

Geminal group-directed olefinic C-H functionalization via four- to eight-membered exo-metallocycles