{"title":"游离醇介导的未活化 C（sp3）-H 键的自由基炔化和烯丙基化。","authors":"Zhu Cao, Yaohui Xu, Zhen Wu, Xinxin Wu, Chen Zhu","doi":"10.1002/chem.202403841","DOIUrl":null,"url":null,"abstract":"<p><p>The daunting challenges in converting alcoholic O-H bonds with high bond-dissociation energy (BDE) to alkoxy radicals and harnessing those unruly reaction species largely limit exploiting free alcohols in C(sp<sup>3</sup>)-H functionalization. Herein we describe a novel radical alkynylation and allylation of unactivated C(sp<sup>3</sup>)-H bonds with unmodified aliphatic alcohols. The use of phenyliodine bis(trifluoroacetate) (PIFA) enables the formation of alkoxy radicals under mild photochemical conditions. α-Methyl styrene serves as a sacrificial-reagent that significantly improves the reaction outcomes. This transition-metal free protocol further features broad substrate scope, exclusive site-selectivity, high product diversity, and simple operation, supplying a robust manifold for C(sp<sup>3</sup>)-H functionalization using easily available aliphatic alcohols as feedstock.</p>","PeriodicalId":144,"journal":{"name":"Chemistry - A European Journal","volume":" ","pages":"e202403841"},"PeriodicalIF":3.9000,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Free Alcohol-Mediated Radical Alkynylation and Allylation of Unactivated C(sp<sup>3</sup>)-H Bonds.\",\"authors\":\"Zhu Cao, Yaohui Xu, Zhen Wu, Xinxin Wu, Chen Zhu\",\"doi\":\"10.1002/chem.202403841\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The daunting challenges in converting alcoholic O-H bonds with high bond-dissociation energy (BDE) to alkoxy radicals and harnessing those unruly reaction species largely limit exploiting free alcohols in C(sp<sup>3</sup>)-H functionalization. Herein we describe a novel radical alkynylation and allylation of unactivated C(sp<sup>3</sup>)-H bonds with unmodified aliphatic alcohols. The use of phenyliodine bis(trifluoroacetate) (PIFA) enables the formation of alkoxy radicals under mild photochemical conditions. α-Methyl styrene serves as a sacrificial-reagent that significantly improves the reaction outcomes. This transition-metal free protocol further features broad substrate scope, exclusive site-selectivity, high product diversity, and simple operation, supplying a robust manifold for C(sp<sup>3</sup>)-H functionalization using easily available aliphatic alcohols as feedstock.</p>\",\"PeriodicalId\":144,\"journal\":{\"name\":\"Chemistry - A European Journal\",\"volume\":\" \",\"pages\":\"e202403841\"},\"PeriodicalIF\":3.9000,\"publicationDate\":\"2024-11-15\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemistry - A European Journal\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1002/chem.202403841\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry - A European Journal","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/chem.202403841","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Free Alcohol-Mediated Radical Alkynylation and Allylation of Unactivated C(sp3)-H Bonds.
The daunting challenges in converting alcoholic O-H bonds with high bond-dissociation energy (BDE) to alkoxy radicals and harnessing those unruly reaction species largely limit exploiting free alcohols in C(sp3)-H functionalization. Herein we describe a novel radical alkynylation and allylation of unactivated C(sp3)-H bonds with unmodified aliphatic alcohols. The use of phenyliodine bis(trifluoroacetate) (PIFA) enables the formation of alkoxy radicals under mild photochemical conditions. α-Methyl styrene serves as a sacrificial-reagent that significantly improves the reaction outcomes. This transition-metal free protocol further features broad substrate scope, exclusive site-selectivity, high product diversity, and simple operation, supplying a robust manifold for C(sp3)-H functionalization using easily available aliphatic alcohols as feedstock.
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Chemistry—A European Journal is a truly international journal with top quality contributions (2018 ISI Impact Factor: 5.16). It publishes a wide range of outstanding Reviews, Minireviews, Concepts, Full Papers, and Communications from all areas of chemistry and related fields.
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