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Accessing Alkoxy Radicals via Frustrated Radical Pairs: Diverse Oxidative Functionalizations of Tertiary Alcohols

Minsoo Ju, Sukwoo Lee, Halle M. Marvich, Song Lin

2024Journal of the American Chemical Society26 citationsDOIOpen Access PDF

Abstract

Alkoxy radicals are versatile reactive intermediates in organic synthesis. Here, we leverage the principle of frustrated radical pair to provide convenient access to these highly reactive species directly from tertiary alcohols via oxoammonium-mediated oxidation of the corresponding alkoxides. This approach enabled various synthetically useful transformations including β-scission, radical cyclization, and remote C-H functionalization, giving rise to versatile alkoxyamines that can be further elaborated to various functionalities.

Topics & Concepts

ChemistryAlkoxy groupRadicalOxidative phosphorylationTertiary alcoholsPhotochemistryOrganic chemistryStereochemistryAlcoholAlkylBiochemistryRadical Photochemical ReactionsOxidative Organic Chemistry ReactionsCatalytic C–H Functionalization Methods