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钯催化环化反应中π-π堆积辅助的区域选择性调控：一项理论研究

π-π stacking assisted regioselectivity regulation in palladium-catalyzed cyclization reactions: a theoretical study.

作者信息

Liu Song, Zhang Dianmin, Gong Yue, Ma Lianli, Li Li, Chen Wei

机构信息

Chongqing Key Laboratory for Resource Utilization of Heavy Metal Wastewater, College of Chemistry and Environmental Engineering, Chongqing University of Arts and Sciences Yongchuan 402160 PR China

School of Chemistry and Chemical Engineering, Chongqing University Chongqing 400030 China.

出版信息

RSC Adv. 2024 Dec 4;14(51):38285-38292. doi: 10.1039/d4ra06552b. eCollection 2024 Nov 25.

DOI:10.1039/d4ra06552b
PMID:39634724
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11615657/
Abstract

The regulation of regioselectivity is an objective often pursued by organic chemists, and the comprehension of its mechanisms is crucial for devising efficient synthetic pathways. In this report, we conducted theoretical calculations to explore the regioselectivity regulatory mechanisms of two palladium-catalyzed cyclization reactions. In these cyclization reactions, manipulating the structural differences in the reaction substrates leads to the formation of distinct products. A detailed reaction mechanism and reactivity profile for this reaction were revealed. Furthermore, a π-π stacking assisted regioselectivity regulatory mechanism was proven by distortion-interaction energy analysis and noncovalent interaction calculations. The calculated results presented herein provide a theoretical guide for further experimental investigations of regioselectivity regulation.

摘要

区域选择性的调控是有机化学家常常追求的目标，而理解其机制对于设计高效的合成途径至关重要。在本报告中，我们进行了理论计算，以探索两个钯催化环化反应的区域选择性调控机制。在这些环化反应中，通过操控反应底物的结构差异可导致形成不同的产物。揭示了该反应详细的反应机理和反应活性概况。此外，通过畸变-相互作用能分析和非共价相互作用计算，证明了一种π-π堆积辅助的区域选择性调控机制。本文给出的计算结果为区域选择性调控的进一步实验研究提供了理论指导。

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