Rhodium(I)-catalyzed reactions via carbon-hydrogen bond cleavage

This chapter focuses on Rh(I)-catalyzed synthetic transformations initiated by carbon-hydrogen (C-H) bond cleavage. The Ru-catalyzed carbonyl-directed C-H alkylation by alkenes is a monumental achievement in organic chemistry. In this reaction, a nitrogen-containing moiety was commonly used as an efficient directing group. Alkynes are conventional coupling partners in C-H activation and alkenylated products are obtained with perfect atom economy. C-H bond cleavage along with carbon-carbon bond-forming reactions provides synthetically useful compounds in one pot. While the metalation of organohalides and subsequent reaction with trialkyl borate is a conventional protocol for the preparation of organoboron compounds, C-H borylation is a more direct and atom-economical approach. Aryl and alkyl silanes are synthetically important because they are functional molecules in themselves and are useful intermediates for further transformations. Among the various approaches to the synthesis of silane-containing compounds, dehydrogenative C-H/Si-H coupling is an atom-economical protocol.