{"title":"铜催化的 2-萘酚不对称脱芳香胺化反应:通过 1,3 还原消除实现 Csp2-N 偶联","authors":"Aying Yihuo, Maoping Pu, Zheng Tan, Jibang Liao, Jiuqi Tan, Qi-Lin Zhou, Xiaohua Liu, Xiaoming Feng","doi":"10.1007/s11426-024-2030-3","DOIUrl":null,"url":null,"abstract":"<p>An efficient catalytic asymmetric dearomatizing amination of 2-naphthols and phenols catalyzed by <i>N,N</i>′-dioxide-copper(I) complex as a chiral catalyst was presented. A variety of optically active <i>β</i>-naphthalenone compounds with a nitrogen-containing quaternary carbon stereocenter were obtained with high yield and enantioselectivity under mild reaction conditions. Mechanistic studies indicated that this Csp<sup>2</sup>–N dearomatizing coupling proceeds <i>via</i> 1,3-reductive elimination of phenolate-Cu<sup>III</sup>-amino intermediate in five-membered ring transition states. The origin of enantioselectivity has also been elucidated based on density functional theory calculations.</p>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":null,"pages":null},"PeriodicalIF":10.4000,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Copper-catalyzed asymmetric dearomatizing amination of 2-naphthols: Csp2–N coupling via 1,3-reductive elimination\",\"authors\":\"Aying Yihuo, Maoping Pu, Zheng Tan, Jibang Liao, Jiuqi Tan, Qi-Lin Zhou, Xiaohua Liu, Xiaoming Feng\",\"doi\":\"10.1007/s11426-024-2030-3\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>An efficient catalytic asymmetric dearomatizing amination of 2-naphthols and phenols catalyzed by <i>N,N</i>′-dioxide-copper(I) complex as a chiral catalyst was presented. A variety of optically active <i>β</i>-naphthalenone compounds with a nitrogen-containing quaternary carbon stereocenter were obtained with high yield and enantioselectivity under mild reaction conditions. Mechanistic studies indicated that this Csp<sup>2</sup>–N dearomatizing coupling proceeds <i>via</i> 1,3-reductive elimination of phenolate-Cu<sup>III</sup>-amino intermediate in five-membered ring transition states. The origin of enantioselectivity has also been elucidated based on density functional theory calculations.</p>\",\"PeriodicalId\":772,\"journal\":{\"name\":\"Science China Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":10.4000,\"publicationDate\":\"2024-07-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Science China Chemistry\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1007/s11426-024-2030-3\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Science China Chemistry","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1007/s11426-024-2030-3","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Copper-catalyzed asymmetric dearomatizing amination of 2-naphthols: Csp2–N coupling via 1,3-reductive elimination
An efficient catalytic asymmetric dearomatizing amination of 2-naphthols and phenols catalyzed by N,N′-dioxide-copper(I) complex as a chiral catalyst was presented. A variety of optically active β-naphthalenone compounds with a nitrogen-containing quaternary carbon stereocenter were obtained with high yield and enantioselectivity under mild reaction conditions. Mechanistic studies indicated that this Csp2–N dearomatizing coupling proceeds via 1,3-reductive elimination of phenolate-CuIII-amino intermediate in five-membered ring transition states. The origin of enantioselectivity has also been elucidated based on density functional theory calculations.
期刊介绍:
Science China Chemistry, co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China and published by Science China Press, publishes high-quality original research in both basic and applied chemistry. Indexed by Science Citation Index, it is a premier academic journal in the field.
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