Theoretical Study of Rh-Catalyzed C–C Bond Formation Through C–H Activation

Abstract

C–C bond formation has attracted enormous research interest and lots of synthesis methods were applied to it in recent years. Accordingly, more and more efforts were put into the theoretical study of Rh-catalyzed C–C bond formation through C–H activation because of the complexity of the C–H bond activation reaction itself and its mechanism. In this chapter, the theoretical studies of Rh-catalyzed C–H bond arylation through electrophiles and nucleophile aryl reagents were first discussed. Subsequently, the mechanisms of C–H bond alkylation by using olefins alkynes and diazo compound along with C–H bond alkenylation by using olefins and alkynes were analyzed from theoretical points of view. The mechanisms of C–H bond alkynylation, C–H bond carbonylation, C–H bond annulation with directing group as electrophile, nucleophile, and internal oxidants were further discussed on account of related contributions. Finally, the mechanisms of the outer-sphere C–H activation, sequential C–H activation, and inner-sphere carbene insertion were theoretically considered to provide a whole picture of the C–C bond formation via C–H activation.