(Invited) Electroreductive C-S and C-O Bond Cleavage in Thioethers and Alcohols

Abstract

Alcohols and thioethers are highly prevalent in both natural and synthetic organic compounds but remain underexplored as starting materials in radical transformations. For this reason, new synthetic methods are highly desirable to unlock the potential of the compound classes. Here, electroreductive cleavage of C-S and C-O bonds in aryl alkyl thioethers and benzylic alcohols is described, along with mechanistic details. The reactions proceed via radical intermediates that, depending on the potential at which they form, may be trapped with electron deficient alkenes in Giese reactions. Alternatively, the open shell intermediates can undergo a radical-polar crossover to the corresponding anions with subsequent protonation or carboxylation to furnish alkanes or arylacetic acid products. Figure 1