72. Yang, D.* Rapid formation of Csp3–Csp3 bonds through copper- catalyzed decarboxylative Csp3–H functionalization

Cui, W.;# Li, Y.;# Li, X.; Li, J.; Song, X.; Lv, J.; Jiang, Y.-Y.;* Chin. Chem. Lett. 2023, 34, 107477. Download Link.

Abstract: Transition-metal-catalyzed decarboxylative and C–H functionalization strategy for the construction of Csp2-Csp2, Csp2-Csp, and Csp2-Csp3 bonds has been extensively studied. However, research surveys of this synthetic strategy for the Csp3-Csp3 bond forming reactions are surprisingly scarce. Herein, we present an efficient approach for the rapid formation of Csp3–Csp3 bond through copper-catalyzed decarboxylative Csp3–H functionalization. The present method should provide a useful access to C3-substituted indole scaffolds with possible biological activities. Mechanistic experiments and DFT calculations supported a dual-Cu(II)-catalytic cycle involving rate-determining decarboxylation in an outer-sphere radical pathway and spin-crossover-promoted C–C bond formation. This strategy offers a promising synthesis method for the construction of Csp3–Csp3 bond in the field of synthetic and pharmaceutical chemistry and extends the number of still limited copper-catalyzed decarboxylative Csp3–Csp3 bond forming reaction.