Dirhodium-Catalyzed Enantioselective B-H Bond Insertion of gem-Diaryl Carbenes: Efficient Access to gem-Diarylmethine Boranes

The scarcity of reliable methods for synthesizing chiral gem-diarylmethine borons limits their applications. Herein, we report a method for highly enantioselective dirhodium-catalyzed B-H bond insertion reactions with diaryl diazomethanes as carbene precursors. These reactions afforded chiral gem-diarylmethine borane compounds in high yield (up to 99 % yield), high activity (turnover numbers up to 14 300), high enantioselectivity (up to 99 % ee) and showed unprecedented broad functional group tolerance. The borane compounds synthesized by this method could be efficiently transformed into diaryl methanol, diaryl methyl amine, and triaryl methane derivatives with good stereospecificity. Mechanistic studies suggested that the borane adduct coordinated to the rhodium catalyst and thus interfered with decomposition of the diazomethane, and that insertion of a rhodium carbene (generated from the diaryl diazomethane) into the B-H bond was most likely the rate-determining step.

Automated summary

A reliable method for synthesizing chiral gem-diarylmethine boron compounds with high yield, high activity, high enantioselectivity, and broad functional group tolerance has been reported. The borane compounds synthesized by this method can be efficiently transformed into various derivatives with good stereospecificity. Mechanistic studies suggest that the coordination of the borane adduct to the rhodium catalyst interferes with the decomposition of the diazomethane, and that insertion of a rhodium carbene into the B-H bond is likely the rate-determining step.