{"title":"光催化1,3-炔与CO2的1,4-碳羧化反应。","authors":"Dong-Sen Duan, , , Fu Cheng, , , Li−Ru Chen, , , Ke-Yang Yu, , , Yu He, , , Chi Wang, , , Wen Bao, , , Dao-Yong Zhu*, , and , Shao-Hua Wang*, ","doi":"10.1021/acs.orglett.5c03750","DOIUrl":null,"url":null,"abstract":"<p >Herein, we report a photocatalytic regioselective 1,4-carbocarboxylation of 1,3-enynes with CO<sub>2</sub> enabled by a thiol-mediated hydrogen atom transfer (HAT) and formate cooperative mechanism. This strategy uses formate and CO<sub>2</sub> as synergistic carbon sources, to deliver a diverse array of aryl-, heteroaryl-, and alkyl-functionalized tetrasubstituted allene carboxylic acids. The reaction exhibits broad substrate scope across electronically and sterically varied enynes and iodides, and facilitates late-stage functionalization of bioactive molecules. Gram-scale synthesis and derivatization experiments further demonstrate its synthetic utility.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 41","pages":"11614–11619"},"PeriodicalIF":5.0000,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Photocatalytic 1,4-Carbocarboxylation of 1,3-Enynes with CO2\",\"authors\":\"Dong-Sen Duan, , , Fu Cheng, , , Li−Ru Chen, , , Ke-Yang Yu, , , Yu He, , , Chi Wang, , , Wen Bao, , , Dao-Yong Zhu*, , and , Shao-Hua Wang*, \",\"doi\":\"10.1021/acs.orglett.5c03750\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Herein, we report a photocatalytic regioselective 1,4-carbocarboxylation of 1,3-enynes with CO<sub>2</sub> enabled by a thiol-mediated hydrogen atom transfer (HAT) and formate cooperative mechanism. This strategy uses formate and CO<sub>2</sub> as synergistic carbon sources, to deliver a diverse array of aryl-, heteroaryl-, and alkyl-functionalized tetrasubstituted allene carboxylic acids. The reaction exhibits broad substrate scope across electronically and sterically varied enynes and iodides, and facilitates late-stage functionalization of bioactive molecules. Gram-scale synthesis and derivatization experiments further demonstrate its synthetic utility.</p>\",\"PeriodicalId\":54,\"journal\":{\"name\":\"Organic Letters\",\"volume\":\"27 41\",\"pages\":\"11614–11619\"},\"PeriodicalIF\":5.0000,\"publicationDate\":\"2025-10-06\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic Letters\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.orglett.5c03750\",\"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://pubs.acs.org/doi/10.1021/acs.orglett.5c03750","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Photocatalytic 1,4-Carbocarboxylation of 1,3-Enynes with CO2
Herein, we report a photocatalytic regioselective 1,4-carbocarboxylation of 1,3-enynes with CO2 enabled by a thiol-mediated hydrogen atom transfer (HAT) and formate cooperative mechanism. This strategy uses formate and CO2 as synergistic carbon sources, to deliver a diverse array of aryl-, heteroaryl-, and alkyl-functionalized tetrasubstituted allene carboxylic acids. The reaction exhibits broad substrate scope across electronically and sterically varied enynes and iodides, and facilitates late-stage functionalization of bioactive molecules. Gram-scale synthesis and derivatization experiments further demonstrate its synthetic utility.
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.