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Iridium‐Catalyzed Asymmetric Allylic Benzylation with Photogenerated Hydroxy‐<i>o</i>‐Quinodimethanes

Pusu Yang, Ruixiang Wang, Yuan‐Zheng Cheng, Chao Zheng, Shu‐Li You

2022Angewandte Chemie International Edition26 citationsDOI

Abstract

An iridium-catalyzed asymmetric allylic benzylation of aryl vinyl carbinols under light irradiation is described. 2-Methylbenzophenone derivatives are employed and activated to hydroxy-o-quinodimethanes by an ultraviolet (UV) light. This approach enables asymmetric allylic benzylation with high enantioselectivity (up to 99 % ee) from readily available 2-methylbenzophenones without the utilization of strong bases, and pre-activation or pre-functionalization of the substrates. Moreover, deuterium experiments reveal the generation of nucleophilic benzyl species from 2-methylbenzophenone under UV irradiation.

Topics & Concepts

IridiumAllylic rearrangementCatalysisChemistryMedicinal chemistryOrganic chemistryCatalytic C–H Functionalization MethodsAsymmetric Synthesis and CatalysisRadical Photochemical Reactions
Iridium‐Catalyzed Asymmetric Allylic Benzylation with Photogenerated Hydroxy‐<i>o</i>‐Quinodimethanes | Litcius