{"title":"P-P 键的结构约束:烯烃、炔烃和羰基的磷化协同机制","authors":"Lijun You, Daniel Roth and Lutz Greb","doi":"10.1039/D4SC06581F","DOIUrl":null,"url":null,"abstract":"<p >Structurally constraining p-block elements has become a powerful strategy for bond activation chemistry with main group compounds. Traditionally, this approach focuses on mononuclear centers, yet applying structural constraints to systems with element–element bonds remains underexplored. In this study, we introduce a cation featuring a structural constraint-elongated P–P bond that spontaneously adds to unactivated alkynes, alkenes, aldehydes, and ketones. Despite its positive charge, the surprisingly apolar P–P<small><sup>+</sup></small> bond promotes phosphinophosphination <em>via</em> a concerted, highly regio- and diastereoselective mechanism. This unique reactivity opens pathways to novel seven-membered phosphorus heterocycles with customizable optical properties and a structurally varied array of ligands for transition metal coordination.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" 4","pages":" 1716-1721"},"PeriodicalIF":7.6000,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/sc/d4sc06581f?page=search","citationCount":"0","resultStr":"{\"title\":\"Structural constraint at a P–P bond: phosphinophosphination of alkenes, alkynes, and carbonyls by a concerted mechanism†\",\"authors\":\"Lijun You, Daniel Roth and Lutz Greb\",\"doi\":\"10.1039/D4SC06581F\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Structurally constraining p-block elements has become a powerful strategy for bond activation chemistry with main group compounds. Traditionally, this approach focuses on mononuclear centers, yet applying structural constraints to systems with element–element bonds remains underexplored. In this study, we introduce a cation featuring a structural constraint-elongated P–P bond that spontaneously adds to unactivated alkynes, alkenes, aldehydes, and ketones. Despite its positive charge, the surprisingly apolar P–P<small><sup>+</sup></small> bond promotes phosphinophosphination <em>via</em> a concerted, highly regio- and diastereoselective mechanism. This unique reactivity opens pathways to novel seven-membered phosphorus heterocycles with customizable optical properties and a structurally varied array of ligands for transition metal coordination.</p>\",\"PeriodicalId\":9909,\"journal\":{\"name\":\"Chemical Science\",\"volume\":\" 4\",\"pages\":\" 1716-1721\"},\"PeriodicalIF\":7.6000,\"publicationDate\":\"2024-11-05\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2025/sc/d4sc06581f?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemical Science\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/sc/d4sc06581f\",\"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":"Chemical Science","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/sc/d4sc06581f","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
对 p 块元素进行结构约束已成为主族化合物键活化化学的有力策略。传统上,这种方法主要针对单核中心,但将结构约束应用于元素-元素键体系的研究仍然不足。在本研究中,我们引入了一种阳离子,它具有结构限制--伸长的 P-P 键,能自发地与未活化的炔、烯、醛和酮相加。尽管它带有正电荷,但令人惊讶的极性 P-P+ 键却能通过一种协同、高度区域和非对映选择性的机制促进磷化作用。这种独特的反应性开辟了通往新型七元磷杂环的道路,这些杂环具有可定制的光学特性,并可配位过渡金属。
Structural constraint at a P–P bond: phosphinophosphination of alkenes, alkynes, and carbonyls by a concerted mechanism†
Structurally constraining p-block elements has become a powerful strategy for bond activation chemistry with main group compounds. Traditionally, this approach focuses on mononuclear centers, yet applying structural constraints to systems with element–element bonds remains underexplored. In this study, we introduce a cation featuring a structural constraint-elongated P–P bond that spontaneously adds to unactivated alkynes, alkenes, aldehydes, and ketones. Despite its positive charge, the surprisingly apolar P–P+ bond promotes phosphinophosphination via a concerted, highly regio- and diastereoselective mechanism. This unique reactivity opens pathways to novel seven-membered phosphorus heterocycles with customizable optical properties and a structurally varied array of ligands for transition metal coordination.
期刊介绍:
Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.