Overcoming O-H Insertion to Para-Selective C-H Functionalization of Free Phenols: Rh(II)/Xantphos Catalyzed Geminal Difunctionalization of Diazo Compounds.

ABSTRACT: Para-selective C-H functionalization of free phenols by metal carbenoids is rather challenging due to the generally more favorable competing O-H insertion. Herein, with the use of the combination of Rh(II) and a Xantphos ligand as the catalyst, a novel multicomponent reaction of free phenols, diazoesters, and allylic carbonates was successfully developed, affording a wide variety of phenol derivatives, bearing an all-carbon quaternary center and a synthetically useful allylic unit. This reaction is likely to occur through a tandem process of carbene-induced para-selective C-H functionalization, followed by Rh(II)/Xantphos-catalyzed allylation. The distinctive reactivity of para-selective C-H rather than O-H insertion for the carbenoid intermediate, combined with featur

SUBMITTER: Yang Y 

PROVIDER: S-EPMC9136979 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature