Carbon‐Centered Radical Addition to OC of Amides or Esters as a Route to CO Bond Formations

Abstract Among various types of radical reactions, the addition of carbon radicals to unsaturated bonds is a powerful tool for constructing new chemical bonds, in which the typical applied unsaturated substrates include alkenes, alkynes and imines. Carbonyl is perhaps the most common unsaturated group in nature. This work demonstrates a novel CO bond formation through carbon‐centered radical addition to the carbonyl oxygen of amide or ester, in which amide and ester groups are easily activated through the radical process. EPR spectroscopy and radical clock experiments support the radical process for this transformation, and density functional theory (DFT) calculations support the possibility of carbon‐centered radical addition to the carbonyl oxygen of amides or esters.