The Duality of Dioxolanyl Radicals towards C–C Bond Construction

Abstract Protecting groups are commonplace in organic synthesis and appear often in the form of dioxanes and dioxolanes. 1,3-Dioxolanes can be used for the protection of both diol and carbonyl motifs. Our group has been increasingly interested in alternative uses for such a simple and often overlooked heterocycle. Herein we highlight recent advancements in dioxolanyl radical chemistry where reactivity can be selectively directed towards two unique positions leading to distinct product formations, resulting in trifluoromethyl ketones and 1,2-diol functionalities. 1 Introduction 2 Dioxolanyl Radicals: Masked Trifluoromethylacetylation 3 Dioxolanyl Radicals: Vicinal Functionality 4 Conclusion and Outlook