Rh(III)-catalyzed C-H activation of aromatic C-H bonds represents a valuable strategy for the synthesis of N-heterocycles. With prominent exceptions, this approach has not been widely used for vinyl C-H bond activation. Moreover, the limited study on cyclopentadienyl ligand derivatives has hindered progress in the field. Herein, we report our recent discovery of N-enoxyphthalimide reactivity.[1] We discovered N-enoxyphthlimides undergo a Rh(III)-catalyzed C-H activation initiated cyclopropanation of electron deficient alkenes. On the basis of our mechanistic study, we propose the transformation involves a directed activation of the olefinic C-H bond followed by two migratory insertions, first across the electon-deficient alkene and again across the enol moiety. The design of a new monosubstituted isopropylcyclopentadienyl ligand allows high diastereoselectivity and yield. Building on these foundations, we are currently exploring other methodologies enabled by the N-enoxypthalamide directing group and ligand design. [1] Piou, T.; Rovis, T. J. Am. Chem. Soc. 2014, 136, 11292-11295

Rh(III)-catalyzed C-H activation of N-enoxyphthalimides

249th National Meeting (2015)

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