{"title":"无过渡金属迭代双倍还原耦合和 1,3-borotropic 移位形成 1,4-skipped 二烯。","authors":"Kasarla Varalaxmi, Kangkan Pradhan, Hasina Mamataj Begam, Arghya Polley, Deepak Kumar, Ranjan Jana","doi":"10.1039/d4ob01389a","DOIUrl":null,"url":null,"abstract":"<p><p>We report herein a transition-metal-free two-fold reductive coupling between prenal (allyl) tosylhydrazone and boronic acids/1,3-borotropic shift cascade to furnish 1,4-skipped dienes. In this work, a single batch operation produces (<i>E</i>,<i>E</i>)-1,4-skipped dienes by undergoing a second reductive coupling of the transient boronic acid, which developed <i>in situ</i> following the first reductive allylation and a cascade 1,3-boron migration. Remarkably, the protocol is compatible with various aryl- and alkyl-substituted boronic acids, is scalable and has demonstrated on 61 substrates with yields up to 98%.</p>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":null,"pages":null},"PeriodicalIF":2.9000,"publicationDate":"2024-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Transition-metal-free iterative two-fold reductive coupling and 1,3-borotropic shift to form 1,4-skipped dienes.\",\"authors\":\"Kasarla Varalaxmi, Kangkan Pradhan, Hasina Mamataj Begam, Arghya Polley, Deepak Kumar, Ranjan Jana\",\"doi\":\"10.1039/d4ob01389a\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>We report herein a transition-metal-free two-fold reductive coupling between prenal (allyl) tosylhydrazone and boronic acids/1,3-borotropic shift cascade to furnish 1,4-skipped dienes. In this work, a single batch operation produces (<i>E</i>,<i>E</i>)-1,4-skipped dienes by undergoing a second reductive coupling of the transient boronic acid, which developed <i>in situ</i> following the first reductive allylation and a cascade 1,3-boron migration. Remarkably, the protocol is compatible with various aryl- and alkyl-substituted boronic acids, is scalable and has demonstrated on 61 substrates with yields up to 98%.</p>\",\"PeriodicalId\":96,\"journal\":{\"name\":\"Organic & Biomolecular Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2024-10-08\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic & Biomolecular Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4ob01389a\",\"RegionNum\":3,\"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 & Biomolecular Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4ob01389a","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Transition-metal-free iterative two-fold reductive coupling and 1,3-borotropic shift to form 1,4-skipped dienes.
We report herein a transition-metal-free two-fold reductive coupling between prenal (allyl) tosylhydrazone and boronic acids/1,3-borotropic shift cascade to furnish 1,4-skipped dienes. In this work, a single batch operation produces (E,E)-1,4-skipped dienes by undergoing a second reductive coupling of the transient boronic acid, which developed in situ following the first reductive allylation and a cascade 1,3-boron migration. Remarkably, the protocol is compatible with various aryl- and alkyl-substituted boronic acids, is scalable and has demonstrated on 61 substrates with yields up to 98%.