Mechanism and Origins of Nucleophile‐Controlled Regioselectivity of Palladium‐Catalyzed Allylic C−H Amination of 1,4‐Dienes: A Computational Study

IF 2.8 4区 化学 Q1 CHEMISTRY, ORGANIC Asian Journal of Organic Chemistry Pub Date : 2024-10-01 DOI:10.1002/ajoc.202400264
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Abstract

Density functional theory calculations have been conducted to investigate the palladium‐catalyzed allylic C−H amination of 1,4‐dienes with commonly available amines. The computations indicate that the reaction begins with the allylic C−H bond cleavage through the concerted proton and two‐electron transfer process to forge the η3‐allyl Pd(II) species. The ensuing C−N bond formation was found to be highly dependent on the basicity of the nucleophile, enabling the regioselectivity switch upon change of the nucleophile. With the weakly basic aromatic amine, the reaction occurs through the hydrogen‐bonding enabled inner‐sphere nucleophilic attack pathway. The distance between the reacting carbon atom and the terminal carbon atom is responsible for the Z/E‐selectivity. The regioselectivity is primarily due to steric repulsion between the allyl group and the ligand. On the other hand, the outer‐sphere nucleophilic attack pathway is favored for the reaction with the more basic aliphatic cyclic amine. The change of the coordinating mode of the allylic moiety was found to play a crucial role in determining the regioselectivity.
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钯催化 1,4-二烯的烯丙基 C-H 氨基化的核亲和剂控制的区域选择性的机理和起源:计算研究
为了研究钯催化的 1,4 二烯与常见胺的烯丙基 C-H 氨化反应,我们进行了密度泛函理论计算。计算结果表明,反应开始时,烯丙基 C-H 键通过质子和双电子协同转移过程裂解,形成 h3-烯丙基 Pd(II) 物种。研究发现,随后形成的 C-N 键与亲核体的碱性有很大关系,因此在改变亲核体时可以实现区域选择性转换。对于弱碱性芳香胺,反应是通过氢键促成的内圈亲核攻击途径发生的。反应碳原子与末端碳原子之间的距离决定了 Z/E 选择性。区域选择性主要是由于烯丙基和配体之间的立体斥力。另一方面,在与碱性较强的脂肪族环胺反应时,外层亲核攻击途径更受青睐。研究发现,烯丙基配位方式的改变在决定区域选择性方面起着至关重要的作用。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
CiteScore
4.70
自引率
3.70%
发文量
372
期刊介绍: Organic chemistry is the fundamental science that stands at the heart of chemistry, biology, and materials science. Research in these areas is vigorous and truly international, with three major regions making almost equal contributions: America, Europe and Asia. Asia now has its own top international organic chemistry journal—the Asian Journal of Organic Chemistry (AsianJOC) The AsianJOC is designed to be a top-ranked international research journal and publishes primary research as well as critical secondary information from authors across the world. The journal covers organic chemistry in its entirety. Authors and readers come from academia, the chemical industry, and government laboratories.
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