{"title":"通过对映体和 Z/E 选择性催化作用立体异构获取非天然 α 氨基酸","authors":"Panpan Li, En Zheng, Guanlin Li, Yicong Luo, Xiaohong Huo, Shengming Ma, Wanbin Zhang","doi":"10.1126/science.ado4936","DOIUrl":null,"url":null,"abstract":"<div >The precise control of <i>Z</i> and <i>E</i> configurations of the carbon-carbon double bond in alkene synthesis has long been a fundamental challenge in synthetic chemistry, even more pronounced when simultaneously striving to achieve enantioselectivity [(<i>Z</i>,<i>R</i>), (<i>Z</i>,<i>S</i>), (<i>E</i>,<i>R</i>), (<i>E</i>,<i>S</i>)]. Moreover, enantiopure non-natural α-amino acids are highly sought after in organic and medicinal chemistry. In this study, we report a ligand-controlled stereodivergent synthesis of non-natural α-quaternary amino acids bearing trisubstituted alkene moieties in high yields with excellent enantioselectivity and <i>Z</i>/<i>E</i> selectivities. This success is achieved through a palladium/copper–cocatalyzed three-component assembly of readily available aryl iodides, allenes, and aldimine esters by simply tuning the chiral ligands of the palladium and copper catalysts.</div>","PeriodicalId":21678,"journal":{"name":"Science","volume":null,"pages":null},"PeriodicalIF":44.7000,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Stereodivergent access to non-natural α-amino acids via enantio- and Z/E-selective catalysis\",\"authors\":\"Panpan Li, En Zheng, Guanlin Li, Yicong Luo, Xiaohong Huo, Shengming Ma, Wanbin Zhang\",\"doi\":\"10.1126/science.ado4936\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div >The precise control of <i>Z</i> and <i>E</i> configurations of the carbon-carbon double bond in alkene synthesis has long been a fundamental challenge in synthetic chemistry, even more pronounced when simultaneously striving to achieve enantioselectivity [(<i>Z</i>,<i>R</i>), (<i>Z</i>,<i>S</i>), (<i>E</i>,<i>R</i>), (<i>E</i>,<i>S</i>)]. Moreover, enantiopure non-natural α-amino acids are highly sought after in organic and medicinal chemistry. In this study, we report a ligand-controlled stereodivergent synthesis of non-natural α-quaternary amino acids bearing trisubstituted alkene moieties in high yields with excellent enantioselectivity and <i>Z</i>/<i>E</i> selectivities. This success is achieved through a palladium/copper–cocatalyzed three-component assembly of readily available aryl iodides, allenes, and aldimine esters by simply tuning the chiral ligands of the palladium and copper catalysts.</div>\",\"PeriodicalId\":21678,\"journal\":{\"name\":\"Science\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":44.7000,\"publicationDate\":\"2024-08-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Science\",\"FirstCategoryId\":\"103\",\"ListUrlMain\":\"https://www.science.org/doi/10.1126/science.ado4936\",\"RegionNum\":1,\"RegionCategory\":\"综合性期刊\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"MULTIDISCIPLINARY SCIENCES\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Science","FirstCategoryId":"103","ListUrlMain":"https://www.science.org/doi/10.1126/science.ado4936","RegionNum":1,"RegionCategory":"综合性期刊","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MULTIDISCIPLINARY SCIENCES","Score":null,"Total":0}
引用次数: 0
摘要
长期以来,在烯烃合成过程中精确控制碳碳双键的 Z 和 E 构型一直是合成化学中的一项基本挑战,当同时努力实现对映选择性[(Z,R), (Z,S), (E,R), (E,S)]时,这一挑战就更加突出。此外,非天然α-氨基酸的对映体纯度也是有机化学和药物化学中亟待解决的问题。在本研究中,我们报告了一种配体控制的立体发散型非天然α-季氨基酸的合成方法,该方法含有三取代烯基,产量高,具有极佳的对映选择性和 Z/E 选择性。只需调整钯和铜催化剂的手性配位体,就能通过钯/铜催化三组分组装现成的芳基碘化物、烯和醛亚胺酯,从而取得这一成功。
Stereodivergent access to non-natural α-amino acids via enantio- and Z/E-selective catalysis
The precise control of Z and E configurations of the carbon-carbon double bond in alkene synthesis has long been a fundamental challenge in synthetic chemistry, even more pronounced when simultaneously striving to achieve enantioselectivity [(Z,R), (Z,S), (E,R), (E,S)]. Moreover, enantiopure non-natural α-amino acids are highly sought after in organic and medicinal chemistry. In this study, we report a ligand-controlled stereodivergent synthesis of non-natural α-quaternary amino acids bearing trisubstituted alkene moieties in high yields with excellent enantioselectivity and Z/E selectivities. This success is achieved through a palladium/copper–cocatalyzed three-component assembly of readily available aryl iodides, allenes, and aldimine esters by simply tuning the chiral ligands of the palladium and copper catalysts.
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