Hydrophilic Iridium Bis-N-Heterocyclic Carbene Complexes Catalyze Linear-Selective, Additive-Free Hydroaminomethylation of Long-Chain Olefins in Water

Yinghao Huo, Xinyi Zhou, Guanfeng Liang, Dr. Xin He, Dr. Qingshu Zheng, Prof.Dr. Tao Tu
{"title":"Hydrophilic Iridium Bis-N-Heterocyclic Carbene Complexes Catalyze Linear-Selective, Additive-Free Hydroaminomethylation of Long-Chain Olefins in Water","authors":"Yinghao Huo,&nbsp;Xinyi Zhou,&nbsp;Guanfeng Liang,&nbsp;Dr. Xin He,&nbsp;Dr. Qingshu Zheng,&nbsp;Prof.Dr. Tao Tu","doi":"10.1002/ange.202508793","DOIUrl":null,"url":null,"abstract":"<p>Aqueous hydroaminomethylation (HAM) of olefins generally requires the use of organic solvents, additives, and high-pressure hydrogen to synthesize amines in satisfactory yields and selectivity. Herein, we accomplish the HAM reactions of long-chain olefins in water without organic solvent or additives by using a hydrophilic bis-NHC-Ir complex as the catalyst. A broad scope of long-chain olefins and amines is well compatible, affording corresponding higher amines in up to 99% yields with excellent linear/branched (<i>l/b</i>) selectivity (up to 94/6). Mechanistic investigations reveal that water acts as both solvent and hydrogen source. The protocol can be readily extended to the synthesis of pharmaceuticals and deuterated analogues with excellent yields and deuterium rates. Moreover, the amine products are easily separated by extraction, and the recovered aqueous phase could be directly used and recycled. This protocol offers a sustainable, safe, and cost-effective approach for synthesizing higher amines.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 41","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie","FirstCategoryId":"1085","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/ange.202508793","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0

Abstract

Aqueous hydroaminomethylation (HAM) of olefins generally requires the use of organic solvents, additives, and high-pressure hydrogen to synthesize amines in satisfactory yields and selectivity. Herein, we accomplish the HAM reactions of long-chain olefins in water without organic solvent or additives by using a hydrophilic bis-NHC-Ir complex as the catalyst. A broad scope of long-chain olefins and amines is well compatible, affording corresponding higher amines in up to 99% yields with excellent linear/branched (l/b) selectivity (up to 94/6). Mechanistic investigations reveal that water acts as both solvent and hydrogen source. The protocol can be readily extended to the synthesis of pharmaceuticals and deuterated analogues with excellent yields and deuterium rates. Moreover, the amine products are easily separated by extraction, and the recovered aqueous phase could be directly used and recycled. This protocol offers a sustainable, safe, and cost-effective approach for synthesizing higher amines.

Abstract Image

亲水铱双- n -杂环羰基配合物在水中催化长链烯烃的线性选择性、无添加剂的氢胺甲基化反应
烯烃的水氢胺甲基化(HAM)通常需要使用有机溶剂、添加剂和高压氢来合成具有满意收率和选择性的胺。本文以亲水的双- nhc - ir配合物为催化剂,在无有机溶剂和添加剂的情况下,完成了长链烯烃在水中的HAM反应。广泛的长链烯烃和胺具有良好的相容性,可提供相应的高胺,收率高达99%,具有良好的线性/支链(l/b)选择性(高达94/6)。机理研究表明,水既是溶剂又是氢源。该方案可以很容易地扩展到药物和氘类似物的合成具有优异的收率和氘率。此外,胺类产物易于萃取分离,回收的水相可直接利用和循环利用。该方案为合成高级胺提供了一种可持续、安全、经济的方法。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
Angewandte Chemie
Angewandte Chemie 化学科学, 有机化学, 有机合成
自引率
0.00%
发文量
0
审稿时长
1 months
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信