Computational study of regiodivergent pathways in the coppercatalyzed borocyanation of 1,3-dienes: Mechanism and origin of regioselectivity
Computational study of regiodivergent pathways in the coppercatalyzed borocyanation of 1,3-dienes: Mechanism and origin of regioselectivity
复制标题
铜催化 1,3-二烯硼氰化反应区域发散路径的计算研究：区域选择性的机制和起源
DOI：
10.1016/j.jorganchem.2019.121014
复制
发表时间：
2019-12-30
影响因子：
2.3
通讯作者：
Li, Juan
中科院分区：
文献类型：
--
作者：
Guo, Xianming;Wang, Ting;Li, Juan
在铜催化的硼氰化的不对称取代的1，3-二烯的区域选择性控制仍然具有挑战性。在这项研究中，我们使用密度泛函理论计算来阐明的起源配体和基板控制的区域选择性。该机制合理化了为什么配体PCy 3有利于1，2-硼铜化，而配体XantPhos有利于2-取代的1，3-二烯的4，3-硼铜化，以及为什么1-取代的，1，2-二取代的，和1，3-二取代的1，3-二烯提供4，3-硼铜化，无论是否存在双齿或单齿配体。在已有实验的基础上，结合其他相关反应的激发，我们尝试通过计算来富集配体和底物。对不同的底物和配体的不同的区域选择性归因于不同的电子和空间因素。(C)2019 Elsevier B. V.版权所有。
Regioselective control in the Cu-catalyzed borylcyanation of nonsymmetrically substituted 1,3-dienes remains challenging. In this study, we used density functional theory calculations to elucidate the origins of ligand- and substrate-controlled regioselectivity. The mechanism rationalizes why ligand PCy3 favors 1,2-borocupration while ligand XantPhos favors 4,3-borocupration for 2-substituted 1,3-dienes, and why 1-substituted, 1,2-disubstituted, and 1,3-disubstituted 1,3-dienes afford 4,3-borocupration, irrespective of the presence of bidentate or monodentate ligands. Based on established experiments and stimulated by other relevant reactions, we attempted to enrich ligands and substrates computationally. The different regioselectivities for different substrates and ligands were attributed to different electronic and steric factors. (C) 2019 Elsevier B.V. All rights reserved.