Construction of All-Carbon Chiral Quaternary Centers through CuI -Catalyzed Enantioselective Reductive Hydroxymethylation of 1,1-Disubstituted Allenes with CO2.

A catalytic enantioselective construction of all-carbon chiral quaternary centers through reductive hydroxymethylation of 1,1-disubstituted allenes with CO2 has been developed. In the presence of a copper/Mandyphos catalyst, CO2 is transformed into an alcohol oxidation level by an asymmetric reductive C-C bond formation with allenes by using hydrosilane (HSi(OMe)2 Me) as a reductant. The resulting chiral homoallylic alcohols are versatile synthetic intermediates and can be conveniently converted into a variety of useful chiral chemicals.