Mn-Mediated α-Radical Addition of Carbonyls to Olefins: Systematic Study, Scope, and Electrocatalysis.

A systematic study of the manganese-mediated α-radical addition of carbonyl groups to olefins is presented. After an in-depth investigation of the parameters that govern the reaction, a first round of optimization allowed the development of a unified stoichiometric set of conditions, which were subsequently assessed during the exploration of the scope. Due to observed limitations, the knowledge accumulated during the initial study was reengaged to quickly optimize promising substrates that were so far inaccessible under previously reported conditions. Altogether these results led to the creation of a predictive model based on the pKa of the carbonyl compound and both the substitution and geometry of the alkene coupling partner. Finally, a departure from the use of stoichiometric manganese was enabled through the development of a robust and practical electrocatalytic version of the reaction.