Computational study on palladium-catalyzed alkenylation of remote δ-C(sp3)-H bonds with alkynes: a new understanding of mechanistic insight and origins of site-selectivity

Hui-Min Yan; Ye Tian; Niu Li; Rong Chang; Zhu-Xia Zhang; Xiao-Yun Zhang; Wen-Jing Yang; Zhen Guo; Yan-Rong Li

doi:10.1039/c8ra06077k

Computational study on palladium-catalyzed alkenylation of remote δ-C(sp³)-H bonds with alkynes: a new understanding of mechanistic insight and origins of site-selectivity

RSC Adv. 2018 Aug 28;8(53):30186-30190. doi: 10.1039/c8ra06077k. eCollection 2018 Aug 24.

Authors

Hui-Min Yan¹, Ye Tian¹, Niu Li¹, Rong Chang¹, Zhu-Xia Zhang¹, Xiao-Yun Zhang¹, Wen-Jing Yang¹, Zhen Guo¹, Yan-Rong Li²

Affiliations

¹ College of Material Science & Engineering, Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology Shanxi 030024 P. R. China [email protected].
² Department of Earth Science and Engineering, Taiyuan University of Technology Shanxi 030024 P. R. China [email protected].

Abstract

Palladium-catalyzed alkenylation of δ-C(sp³)-H bonds with alkynes was conducted by density functional theory calculations. The present study shows that the dimeric Pd₂(OAc)₄ mechanism reproduces experimental observations well, including regioselectivity and provides a deep mechanistic insight complementing the monomeric Pd(OAc)₂ mechanism recently reported by Chen's group. In addition, the economical heterodimeric Ni-Pd(OAc)₄ was predicted to be a potential species for such alkenylation of δ-C(sp³)-H bonds.