Access to α-Cyano Carbonyls Bearing a Quaternary Carbon Center by Reductive Cyanation

Reductive cyanation of tertiary alkyl bromides using electrophilic cyanating reagent and zinc reductant was developed, providing various alpha-cyano ketones, esters, and carboxamides containing a nitrile-bearing all-carbon quaternary center in good to excellent yields under mild reaction conditions. The corresponding reaction mechanism involving in situ generated organozinc reagent and reactivity distinction was elucidated by density functional theory computation.

Automated summary

A method for reductive cyanation of tertiary alkyl bromides was developed, providing good to excellent yields of various alpha-cyano ketones, esters, and carboxamides containing a nitrile-bearing all-carbon quaternary center under mild reaction conditions. The corresponding reaction mechanism involving in situ generated organozinc reagent and reactivity distinction was elucidated by density functional theory computation.