{"title":"Stereodivergent 3,4-Hydroalkoxylation of 1,3-Dienes Via Dual Photo and Copper Catalysis","authors":"Yuan Jin, Yanpu Li, Jiarui Tang, Ziyuan Wang, Jianhui Chen*, Zhaoqian Zhang and Biao Cheng*, ","doi":"10.1021/acs.orglett.5c03016","DOIUrl":null,"url":null,"abstract":"<p >We developed a photocatalytic copper-catalyzed stereodivergent 3,4-hydroalkoxylation of 1,3-dienes. By simply controlling reaction time, this protocol selectively affords either <i>E</i>- or <i>Z</i>-allylic ethers in moderate to excellent yields with high stereoselectivity (up to >20/1). The transformation demonstrates remarkable scalability, maintaining excellent stereocontrol even at gram-scale operations. Preliminary mechanistic studies reveal: (1) initial SET reduction generates key diene radical anion intermediates, (2) a synergistic photoredox/copper catalytic manifold directs <i>E</i>-selectivity, and (3) prolonged irradiation induces EnT-mediated photoisomerization to the <i>Z</i>-products.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 36","pages":"10000–10005"},"PeriodicalIF":5.0000,"publicationDate":"2025-09-01","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.5c03016","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
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Abstract
We developed a photocatalytic copper-catalyzed stereodivergent 3,4-hydroalkoxylation of 1,3-dienes. By simply controlling reaction time, this protocol selectively affords either E- or Z-allylic ethers in moderate to excellent yields with high stereoselectivity (up to >20/1). The transformation demonstrates remarkable scalability, maintaining excellent stereocontrol even at gram-scale operations. Preliminary mechanistic studies reveal: (1) initial SET reduction generates key diene radical anion intermediates, (2) a synergistic photoredox/copper catalytic manifold directs E-selectivity, and (3) prolonged irradiation induces EnT-mediated photoisomerization to the Z-products.
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.
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