Deoxygenative functionalization of alcohols, ethers, and carbonyl compounds by chromium catalysis.

The development of an efficient and unified methodology for converting ubiquitous alcohols, ethers, carbonyls, and esters into value-added products via the activation of C-O single and double bonds is of great interest and importance but remains a challenging goal. Herein, we report an efficient and general chromium-catalyzed strategy for the deoxygenative functionalization of alcohols, ethers, and carbonyl compounds with a number of electrophiles. This general strategy couples these oxygenated functional groups with a number of electrophiles, providing an efficient route for the synthesis of a broad range of synthetically appealing organosilicon, organogermanium, organostannane, and organoboron compounds. Moreover, this chromium-catalyzed strategy is demonstrated to be readily scalable and applicable to the late-stage functionalization of various biorelevant molecules. Mechanistic investigations suggest that this deoxygenative functionalization was initiated by two-electron oxidative addition of the C-O bond to a highly active, low-valent chromium species, generating an organochromium intermediate that reacts with a number of electrophiles to construct C-Si, C-Ge, C-Sn, and C-B bonds.