O‐Alkyl S‐3,3‐Dimethyl‐2‐oxobutyl Dithiocarbonates as Versatile Sulfur‐Transfer Agents in Radical C(sp3)H Functionalization

Boiling of the title compounds in ethereal solvents or cycloalkanes in the presence of a radical initiator leads to radical C(sp3)-H functionalization, by which a sulfur atom is introduced into the ethereal solvents at the oxygenated carbon atom or into the cycloalkanes. Both acyclic and cyclic ethers, such as [18]crown-6 and [D8]THF, undergo the sulfur transfer. The reaction is useful for the synthesis of monothioacetals, thiols, and sulfides from simple starting materials.