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
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.
Authors
- Xiao‐Song Xue (ORCID: https://orcid.org/0000-0003-4541-8702)
- Yangang Liu (ORCID: https://orcid.org/0000-0003-0238-0468)
- Shuo Guo (ORCID: https://orcid.org/0000-0002-3042-9209)
- Haibing Yang (ORCID: https://orcid.org/0000-0003-1642-5698)
- Hao Zhang (ORCID: https://orcid.org/0000-0003-2249-3179)
- Jiayu Li (ORCID: https://orcid.org/0000-0002-5204-5310)
- Wei Zhang (ORCID: https://orcid.org/0000-0003-3765-4908)
- Gang Wu (ORCID: https://orcid.org/0000-0003-0442-7469)
- Meng‐Meng Zheng (ORCID: https://orcid.org/0000-0002-4890-9921)
- Donglei Sun (ORCID: https://orcid.org/0000-0002-3827-3982)
- Shuangqing Yue
Institutions
- Sichuan University (CN)
- Inner Mongolia University (CN)
- Shanghai Institute of Organic Chemistry (CN)
- Institute for Advanced Study (DE)
- University of Chinese Academy of Sciences (CN)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-07-16
- DOI
- https://doi.org/10.1021/jacs.5c09085
- Citations
- 6
- Primary Topic
- Fluorine in Organic Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 4.74
Funders
- National Natural Science Foundation of China
- Chinese Academy of Sciences
- Natural Science Foundation of Inner Mongolia
- Department of Science and Technology of Sichuan Province
- Postdoctoral Science Foundation of Shanghai Municipality