{"title":"Mechanism and Origins of Nucleophile‐Controlled Regioselectivity of Palladium‐Catalyzed Allylic C−H Amination of 1,4‐Dienes: A Computational Study","authors":"Mengyao Zhang , Shiyu Wang , Hongli Wu , Genping Huang","doi":"10.1002/ajoc.202400264","DOIUrl":null,"url":null,"abstract":"<div><div>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 η<sup>3</sup>‐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 <em>Z</em>/<em>E</em>‐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.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 10","pages":"Article e202400264"},"PeriodicalIF":2.8000,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Asian Journal of Organic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S2193580724003246","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0
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.
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.