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钯催化末端δ-C(sp)-H键与炔烃的烯基化反应的计算研究：对反应机理及位点选择性起源的新认识

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

作者信息

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

机构信息

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

Department of Earth Science and Engineering, Taiyuan University of Technology Shanxi 030024 P. R. China

出版信息

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

DOI:10.1039/c8ra06077k
PMID:35546853
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9085394/
Abstract

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

摘要

通过密度泛函理论计算研究了钯催化的δ-C(sp)-H键与炔烃的烯基化反应。本研究表明，二聚体Pd(OAc)机理能很好地重现实验观察结果，包括区域选择性，并提供了深入的机理见解，补充了陈课题组最近报道的单体Pd(OAc)机理。此外，经济的异二聚体Ni-Pd(OAc)被预测为δ-C(sp)-H键烯基化反应的潜在物种。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0626/9085394/0ac95c9a4ca4/c8ra06077k-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0626/9085394/5b0174bb240f/c8ra06077k-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0626/9085394/87dd5cf83c4d/c8ra06077k-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0626/9085394/60cc82cc2289/c8ra06077k-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0626/9085394/0ac95c9a4ca4/c8ra06077k-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0626/9085394/5b0174bb240f/c8ra06077k-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0626/9085394/87dd5cf83c4d/c8ra06077k-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0626/9085394/60cc82cc2289/c8ra06077k-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0626/9085394/0ac95c9a4ca4/c8ra06077k-f2.jpg

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本文引用的文献

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Unraveling innate substrate control in site-selective palladium-catalyzed C-H heterocycle functionalization.解析位点选择性钯催化C-H杂环官能化中的固有底物控制
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定向 C(sp ²)-H 功能化的补充策略：过渡金属催化活化、氢原子转移和卡宾/氮烯转移的比较。
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