C-Methylenation of anilines and indoles with CO2 and hydrosilane using a pentanuclear zinc complex catalyst

The one-step C-methylenation of anilines and indoles with CO2 and phenylsilane was catalyzed by a pentanuclear Zn-II complex to give diarylmethanes via geminal C-H and C-C bond formation. It is proposed that the zinc-hydride complex generated in situ is a catalytically active species and that bis(silyl)acetal is a key intermediate. When aniline was used as a substrate, both the C-methylenation and N-methylation proceeded.

Automated summary

A pentanuclear zinc complex catalyzed the one-step C-methylenation of anilines and indoles with CO2 and phenylsilane to form diarylmethanes. The zinc-hydride complex generated in situ is proposed as the catalytically active species, with bis(silyl)acetal identified as a key intermediate in the reaction mechanism. Using aniline as a substrate, both C-methylenation and N-methylation were observed.