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Direct Benzylic C(sp<sup>3</sup>)–O Coupling with Alcohol via Site-Selective C(sp<sup>3</sup>)–H Cleavage at Room Temperature through a Remote Directing Group-Enabled Radical Relay Strategy

Fang Wang, Jiaming Chen, Xiaoqi Jia, Dailin Zhuang, Zhenyang Wan, Lifang Ma, Ziyuan Li

2022The Journal of Organic Chemistry10 citationsDOI

Abstract

Employing a low loading of the terminal oxidant, a remote directing group-enabled radical relay strategy for benzylic direct C(sp3)–H alkoxylation with alcohols at room temperature is developed. Satisfactory site-selectivity, chemoselectivity, and reaction scope are achieved under simple and mild conditions, and no ligand or additive is required. Mechanistic studies, ready conversions of the directing group, and other benzylic functionalizations currently under development in our laboratory further indicate the promising potentials of this remote directing group-enabled radical relay strategy.

Topics & Concepts

ChemoselectivityChemistryRelaySelectivityCleavage (geology)AlcoholPhotochemistryLigand (biochemistry)RadicalCombinatorial chemistryStereochemistryMedicinal chemistryOrganic chemistryCatalysisReceptorFracture (geology)PhysicsPower (physics)EngineeringBiochemistryGeotechnical engineeringQuantum mechanicsCatalytic C–H Functionalization MethodsRadical Photochemical ReactionsOxidative Organic Chemistry Reactions
Direct Benzylic C(sp<sup>3</sup>)–O Coupling with Alcohol via Site-Selective C(sp<sup>3</sup>)–H Cleavage at Room Temperature through a Remote Directing Group-Enabled Radical Relay Strategy | Litcius