Betaine Catalysis for Hierarchical Reduction of CO2 with Amines and Hydrosilane To Form Formamides, Aminals, and Methylamines

An efficient, sustainable organocatalyst, glycine betaine, was developed for the reductive functionalization of CO2 with amines and diphenylsilane. Methylamines and formamides were obtained in high yield by tuning the CO2 pressure and reaction temperature. Based on identification of the key intermediate, that is, the aminal, an alternative mechanism for methylation involving the C0 silyl acetal and aminal is proposed. Furthermore, reducing the CO2 amount afforded aminals with high yield and selectivity. Therefore, betaine catalysis affords products with a diversified energy content that is, formamides, aminals and methylamines, by hierarchical two‐, four‐ and six‐electron reduction, respectively, of CO2 coupled with C−N bond formation.