{"title":"通过铑催化β,β-二取代的烯砜酰胺的烯丙基烷基化反应立体选择性地构建较难获得的无环季碳立体中心点","authors":"Gaoqiang You, Chong-Dao Lu","doi":"10.1021/acs.orglett.4c03043","DOIUrl":null,"url":null,"abstract":"In the presence of Wilkinson’s catalyst, the <i>N</i>-sulfinyl metalloenamines derived from NH-deprotonation of β,β-disubstituted enesulfinamides undergo nucleophilic allylic substitution with allyl carbonate, affording α-allylated ketimines with high stereoselectivity. These allylation products possess challenging acyclic quaternary stereocenters containing one allyl group and two alkyl groups that are both sterically and electronically similar (<i>e.g</i>., Me and Et). By utilizing appropriate stereoisomers of enesulfinamides, it becomes feasible to selectively access each of the four potential stereoisomers of the allylation products, thereby facilitating the selective synthesis of stereoisomers of α-tertiary chiral amines featuring a β-quaternary stereocenter through imino nucleophilic addition.","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":null,"pages":null},"PeriodicalIF":4.9000,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Stereoselective Construction of Less-Accessible Acyclic Quaternary Carbon Stereocenters via Rhodium-Catalyzed Allylic Alkylation of β,β-Disubstituted Enesulfinamides\",\"authors\":\"Gaoqiang You, Chong-Dao Lu\",\"doi\":\"10.1021/acs.orglett.4c03043\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"In the presence of Wilkinson’s catalyst, the <i>N</i>-sulfinyl metalloenamines derived from NH-deprotonation of β,β-disubstituted enesulfinamides undergo nucleophilic allylic substitution with allyl carbonate, affording α-allylated ketimines with high stereoselectivity. These allylation products possess challenging acyclic quaternary stereocenters containing one allyl group and two alkyl groups that are both sterically and electronically similar (<i>e.g</i>., Me and Et). By utilizing appropriate stereoisomers of enesulfinamides, it becomes feasible to selectively access each of the four potential stereoisomers of the allylation products, thereby facilitating the selective synthesis of stereoisomers of α-tertiary chiral amines featuring a β-quaternary stereocenter through imino nucleophilic addition.\",\"PeriodicalId\":54,\"journal\":{\"name\":\"Organic Letters\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.9000,\"publicationDate\":\"2024-10-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic Letters\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.orglett.4c03043\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic Letters","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.orglett.4c03043","RegionNum":1,"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
摘要
在威尔金森催化剂的作用下,β,β-二取代烯磺酰胺经 NH-脱质子反应生成的 N-亚磺酰金属烯胺会与碳酸烯丙基酯发生亲核烯丙基取代反应,从而以高立体选择性生成α-烯丙基酮亚胺。这些烯丙基化产物具有具有挑战性的无环四元立体中心,其中包含一个烯丙基和两个立体和电子相似的烷基(如 Me 和 Et)。利用适当的烯磺酰胺立体异构体,可以选择性地获得烯丙基化产物的四种潜在立体异构体中的每一种,从而促进了通过亚氨基亲核加成法选择性地合成具有 β 季立体中心的 α-叔手性胺的立体异构体。
Stereoselective Construction of Less-Accessible Acyclic Quaternary Carbon Stereocenters via Rhodium-Catalyzed Allylic Alkylation of β,β-Disubstituted Enesulfinamides
In the presence of Wilkinson’s catalyst, the N-sulfinyl metalloenamines derived from NH-deprotonation of β,β-disubstituted enesulfinamides undergo nucleophilic allylic substitution with allyl carbonate, affording α-allylated ketimines with high stereoselectivity. These allylation products possess challenging acyclic quaternary stereocenters containing one allyl group and two alkyl groups that are both sterically and electronically similar (e.g., Me and Et). By utilizing appropriate stereoisomers of enesulfinamides, it becomes feasible to selectively access each of the four potential stereoisomers of the allylation products, thereby facilitating the selective synthesis of stereoisomers of α-tertiary chiral amines featuring a β-quaternary stereocenter through imino nucleophilic addition.
期刊介绍:
Organic Letters invites original reports of fundamental research in all branches of the theory and practice of organic, physical organic, organometallic,medicinal, and bioorganic chemistry. Organic Letters provides rapid disclosure of the key elements of significant studies that are of interest to a large portion of the organic community. In selecting manuscripts for publication, the Editors place emphasis on the originality, quality and wide interest of the work. Authors should provide enough background information to place the new disclosure in context and to justify the rapid publication format. Back-to-back Letters will be considered. Full details should be reserved for an Article, which should appear in due course.