{"title":"β，γ-不饱和酮通过伴随的1,2-羰基迁移的自由基1,3-双官能化：β- sf5 -/β- cf3sf4酮的入口。","authors":"Jia-Yu Li, Ying Liu, Donglei Sun, Gang Wu, Shuai-Shuai Yue, Hui-Yi Yang, Hao Zhang, Wei Zhang, Meng-Meng Zheng, Xiao-Song Xue, Shuo Guo","doi":"10.1021/jacs.5c09085","DOIUrl":null,"url":null,"abstract":"<p><p>The radical migration (RaM) mechanism via photoinduced transformation is a powerful tool in organic synthesis to construct new molecular scaffolds. Herein we disclose a metal-free, photoinduced 1,2-carbonyl migration of β,γ-unsaturated ketones to afford a wide range of valuable β-SF<sub>5</sub>/β-CF<sub>3</sub>SF<sub>4</sub> ketones. This transformation exhibits broad functional group tolerance and is suitable for the late-stage modification of complex molecules in up to 93% yield with excellent chemoselectivity and regioselectivity. Furthermore, mechanistic studies reveal that the selective synthesis of 1,3-chloropentafluorosulfanylation can be accomplished via a carbonyl migration followed by a radical chain propagation pathway. Finally, SF<sub>5</sub>-containing compound <b>5</b> exhibits potential anticancer activity, underscoring the utility of this approach.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"26124-26132"},"PeriodicalIF":15.6000,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Radical 1,3-Difunctionalization of β,γ-Unsaturated Ketones via Concomitant 1,2-Carbonyl Migration: An Entrance to β-SF<sub>5</sub>-/β-CF<sub>3</sub>SF<sub>4</sub> Ketones.\",\"authors\":\"Jia-Yu Li, Ying Liu, Donglei Sun, Gang Wu, Shuai-Shuai Yue, Hui-Yi Yang, Hao Zhang, Wei Zhang, Meng-Meng Zheng, Xiao-Song Xue, Shuo Guo\",\"doi\":\"10.1021/jacs.5c09085\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The radical migration (RaM) mechanism via photoinduced transformation is a powerful tool in organic synthesis to construct new molecular scaffolds. Herein we disclose a metal-free, photoinduced 1,2-carbonyl migration of β,γ-unsaturated ketones to afford a wide range of valuable β-SF<sub>5</sub>/β-CF<sub>3</sub>SF<sub>4</sub> ketones. This transformation exhibits broad functional group tolerance and is suitable for the late-stage modification of complex molecules in up to 93% yield with excellent chemoselectivity and regioselectivity. Furthermore, mechanistic studies reveal that the selective synthesis of 1,3-chloropentafluorosulfanylation can be accomplished via a carbonyl migration followed by a radical chain propagation pathway. Finally, SF<sub>5</sub>-containing compound <b>5</b> exhibits potential anticancer activity, underscoring the utility of this approach.</p>\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":\" \",\"pages\":\"26124-26132\"},\"PeriodicalIF\":15.6000,\"publicationDate\":\"2025-07-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/jacs.5c09085\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2025/7/16 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jacs.5c09085","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/7/16 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Radical 1,3-Difunctionalization of β,γ-Unsaturated Ketones via Concomitant 1,2-Carbonyl Migration: An Entrance to β-SF5-/β-CF3SF4 Ketones.
The radical migration (RaM) mechanism via photoinduced transformation is a powerful tool in organic synthesis to construct new molecular scaffolds. Herein we disclose a metal-free, photoinduced 1,2-carbonyl migration of β,γ-unsaturated ketones to afford a wide range of valuable β-SF5/β-CF3SF4 ketones. This transformation exhibits broad functional group tolerance and is suitable for the late-stage modification of complex molecules in up to 93% yield with excellent chemoselectivity and regioselectivity. Furthermore, mechanistic studies reveal that the selective synthesis of 1,3-chloropentafluorosulfanylation can be accomplished via a carbonyl migration followed by a radical chain propagation pathway. Finally, SF5-containing compound 5 exhibits potential anticancer activity, underscoring the utility of this approach.
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The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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