Phosphine oxide directing-group-enabled atroposelective C-H bond acyloxylation via an eight-membered palladacycle intermediate

Herein, we report the first atroposelective C(sp2)-H bond acyloxylation enabled by a phosphine oxide di-recting group. Uniquely, this transformation is shown to proceed through an eight-membered palladacycle intermediate, as opposed to the kinetically and thermodynamically favored five-membered palladacycle intermediate. Additionally, L-pGlu-OH, a cheap and abundant chiral amino acid derivative, was identified as the best chiral ligand to promote this atroposelective remote C -H functionalization reaction. (c) 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Automated summary

Here, we present the first atroposelective acyloxylation of a C(sp2)-H bond using a phosphine oxide directing group. Surprisingly, this reaction proceeds via an eight-membered palladacycle intermediate instead of the more favored five-membered palladacycle. Additionally, we found that L-pGlu-OH, a readily available chiral amino acid derivative, is the best chiral ligand for promoting this atroposelective remote C-H functionalization reaction.