Shao-Jie Lou, Pan Wang, Xin Wen, Aniket Mishra, Xuefeng Cong, Qingde Zhuo, Kun An, Masayoshi Nishiura, Yi Luo, Zhaomin Hou
{"title":"通过钪催化烯丙基 C-H 活化实现 1,1-二取代烯烃的 (Z)-选择性异构化","authors":"Shao-Jie Lou, Pan Wang, Xin Wen, Aniket Mishra, Xuefeng Cong, Qingde Zhuo, Kun An, Masayoshi Nishiura, Yi Luo, Zhaomin Hou","doi":"10.1021/jacs.4c06899","DOIUrl":null,"url":null,"abstract":"The isomerization of 1,1-disubstituted alkenes through 1,3-hydrogen shift is an atom-efficient route for synthesizing trisubstituted alkenes, which are important moieties in many natural products, pharmaceuticals, and organic materials. However, this reaction often encounters regio- and stereoselectivity challenges, typically yielding <i>E</i>/<i>Z</i>-mixtures of the alkene products or thermodynamically favored (<i>E</i>)-alkenes. Herein, we report the (<i>Z</i>)-selective isomerization of 1,1-disubstituted alkenes to trisubstituted (<i>Z</i>)-alkenes via the regio- and stereospecific activation of an allylic C–H bond. The key to the success of this unprecedented transformation is the use of a sterically demanding half-sandwich scandium catalyst in combination with a bulky quinoline compound, 2-<i>tert</i>-butylquinoline. Deuterium-labeling experiments and density functional theory (DFT) calculations have revealed that 2-<i>tert</i>-butylquinoline not only facilitates the C═C bond transposition through hydrogen shuttling but also governs the regio- and stereoselectivity due to the steric hindrance of the <i>tert</i>-butyl group. This protocol enables the synthesis of diverse (<i>Z</i>)-configured acyclic trisubstituted alkenes and endocyclic trisubstituted alkenes from readily accessible 1,1-disubstituted alkenes. It offers an efficient and selective route for preparing a new family of synthetically challenging (<i>Z</i>)-trisubstituted alkenes with broad substrate scope, 100% atom efficiency, high regio- and stereoselectivity, and an unprecedented reaction mechanism.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"10 1","pages":""},"PeriodicalIF":14.4000,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"(Z)-Selective Isomerization of 1,1-Disubstituted Alkenes by Scandium-Catalyzed Allylic C–H Activation\",\"authors\":\"Shao-Jie Lou, Pan Wang, Xin Wen, Aniket Mishra, Xuefeng Cong, Qingde Zhuo, Kun An, Masayoshi Nishiura, Yi Luo, Zhaomin Hou\",\"doi\":\"10.1021/jacs.4c06899\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The isomerization of 1,1-disubstituted alkenes through 1,3-hydrogen shift is an atom-efficient route for synthesizing trisubstituted alkenes, which are important moieties in many natural products, pharmaceuticals, and organic materials. However, this reaction often encounters regio- and stereoselectivity challenges, typically yielding <i>E</i>/<i>Z</i>-mixtures of the alkene products or thermodynamically favored (<i>E</i>)-alkenes. Herein, we report the (<i>Z</i>)-selective isomerization of 1,1-disubstituted alkenes to trisubstituted (<i>Z</i>)-alkenes via the regio- and stereospecific activation of an allylic C–H bond. The key to the success of this unprecedented transformation is the use of a sterically demanding half-sandwich scandium catalyst in combination with a bulky quinoline compound, 2-<i>tert</i>-butylquinoline. Deuterium-labeling experiments and density functional theory (DFT) calculations have revealed that 2-<i>tert</i>-butylquinoline not only facilitates the C═C bond transposition through hydrogen shuttling but also governs the regio- and stereoselectivity due to the steric hindrance of the <i>tert</i>-butyl group. This protocol enables the synthesis of diverse (<i>Z</i>)-configured acyclic trisubstituted alkenes and endocyclic trisubstituted alkenes from readily accessible 1,1-disubstituted alkenes. It offers an efficient and selective route for preparing a new family of synthetically challenging (<i>Z</i>)-trisubstituted alkenes with broad substrate scope, 100% atom efficiency, high regio- and stereoselectivity, and an unprecedented reaction mechanism.\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":\"10 1\",\"pages\":\"\"},\"PeriodicalIF\":14.4000,\"publicationDate\":\"2024-09-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/jacs.4c06899\",\"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":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jacs.4c06899","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
(Z)-Selective Isomerization of 1,1-Disubstituted Alkenes by Scandium-Catalyzed Allylic C–H Activation
The isomerization of 1,1-disubstituted alkenes through 1,3-hydrogen shift is an atom-efficient route for synthesizing trisubstituted alkenes, which are important moieties in many natural products, pharmaceuticals, and organic materials. However, this reaction often encounters regio- and stereoselectivity challenges, typically yielding E/Z-mixtures of the alkene products or thermodynamically favored (E)-alkenes. Herein, we report the (Z)-selective isomerization of 1,1-disubstituted alkenes to trisubstituted (Z)-alkenes via the regio- and stereospecific activation of an allylic C–H bond. The key to the success of this unprecedented transformation is the use of a sterically demanding half-sandwich scandium catalyst in combination with a bulky quinoline compound, 2-tert-butylquinoline. Deuterium-labeling experiments and density functional theory (DFT) calculations have revealed that 2-tert-butylquinoline not only facilitates the C═C bond transposition through hydrogen shuttling but also governs the regio- and stereoselectivity due to the steric hindrance of the tert-butyl group. This protocol enables the synthesis of diverse (Z)-configured acyclic trisubstituted alkenes and endocyclic trisubstituted alkenes from readily accessible 1,1-disubstituted alkenes. It offers an efficient and selective route for preparing a new family of synthetically challenging (Z)-trisubstituted alkenes with broad substrate scope, 100% atom efficiency, high regio- and stereoselectivity, and an unprecedented reaction mechanism.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.