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Chemoselective Cross-Coupling between Two Different and Unactivated C(aryl)–O Bonds Enabled by Chromium Catalysis

Jinghua Tang, Liu Leo Liu, Shangru Yang, Xuefeng Cong, Meiming Luo, Xiaoming Zeng

2020Journal of the American Chemical Society80 citationsDOI

Abstract

We report here the first example of cross-coupling between two different and unactivated C(aryl)–O bonds with chromium catalysis. The combination of a low-cost Cr(II) salt, 4,4′-di-tert-butyl-2,2′-dipyridyl (dtbpy) as the ligand, and magnesium as the reductant shows high reactivity in promoting the reductive cross-coupling of aryl methyl ether derivatives with aryl esters by cleavage and coupling of two different C(aryl)–O bonds under mild conditions. The formation of active low-valent Cr species by reduction of CrCl2 with Mg can be considered, which prefers to initially activate the C(aryl)–O bond of phenyl methyl ether with the chelation help of dtbpy and an o-imine auxiliary. The subsequent consecutive reduction, second C(aryl)–O activation, and reductive elimination allow for the achievement of selective cross-coupling of C(aryl)–O/C(aryl)–O bonds.

Topics & Concepts

ChemistryArylMedicinal chemistryCatalysisReductive eliminationEtherImineChromiumBond cleavageCoupling reactionLigand (biochemistry)StereochemistryOrganic chemistryBiochemistryReceptorAlkylCatalytic Cross-Coupling ReactionsCatalytic C–H Functionalization MethodsRadical Photochemical Reactions
Chemoselective Cross-Coupling between Two Different and Unactivated C(aryl)–O Bonds Enabled by Chromium Catalysis | Litcius