Geminal Difunctionalizations of Aliphatic Ketones and Aldehydes Enabled by Thioacetal Activation and Deep Electroreduction.

In this work, we identify dithioacetals as synthetically accessible, redox-active, and traceless activating groups that enable the electroreductive transformation of aliphatic ketones and aldehydes. This strategy effectively converts these carbonyl compounds into dianion equivalents to undergo deoxygenative gem-difunctionalization with various electrophiles. Faradaic control was achieved over reaction chemoselectivity, allowing for the combinatorial construction of densely functionalized silanes, boronates, and germanes.