Divergent Synthesis of Trifluoromethyl Ketones via Photoredox Activation of Halotrifluoroacetones

IF 1.5 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Helvetica Chimica Acta Pub Date : 2024-09-25 DOI:10.1002/hlca.202400125
Rahul Giri, Mathias Kissling, Egor Zhilin, Anthony J. Fernandes, Quentin E. L. Ordan, Dmitry Katayev
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Abstract

Fluorine's high electronegativity, lipophilicity, and metabolic stability make it a valuable element for drug design and development. Consequently, significant synthetic efforts have focused on introducing fluorine and fluorinated motifs into organic molecules, with the synthesis of trifluoromethyl ketones (TFMKs) recently attracting considerable attention. Building on our ongoing research on radical organofluorine chemistry, we present herein the divergent synthesis of trifluoromethyl ketones directly from olefins using readily available chloro- and bromotrifluoroacetone as synthetic precursors of the trifluoroacetonyl radical under photoredox catalysis. Mechanistic studies revealed that the divergence is attained through radical polar crossover (RPC) and hydrogen atom transfer (HAT) mechanisms.

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通过光氧化活化卤代三氟丙酮分歧合成三氟甲基酮
氟的高电负性、亲油性和代谢稳定性使其成为药物设计和开发的重要元素。因此,大量合成工作都集中在将氟和氟化基团引入有机分子中,其中三氟甲基酮(TFMKs)的合成最近引起了广泛关注。在我们正在进行的有机氟自由基化学研究的基础上,我们在此介绍在光氧化催化下,使用现成的氯三氟丙酮和溴三氟丙酮作为三氟丙酮自由基的合成前体,直接从烯烃中发散合成三氟甲基酮。机理研究表明,分歧是通过自由基极性交叉(RPC)和氢原子转移(HAT)机理实现的。
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来源期刊
Helvetica Chimica Acta
Helvetica Chimica Acta 化学-化学综合
CiteScore
3.00
自引率
0.00%
发文量
60
审稿时长
2.3 months
期刊介绍: Helvetica Chimica Acta, founded by the Swiss Chemical Society in 1917, is a monthly multidisciplinary journal dedicated to the dissemination of knowledge in all disciplines of chemistry (organic, inorganic, physical, technical, theoretical and analytical chemistry) as well as research at the interface with other sciences, where molecular aspects are key to the findings. Helvetica Chimica Acta is committed to the publication of original, high quality papers at the frontier of scientific research. All contributions will be peer reviewed with the highest possible standards and published within 3 months of receipt, with no restriction on the length of the papers and in full color.
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Cover Picture: (Helv. Chim. Acta 11/2024) The pKa of Water and the Fundamental Laws Describing Solution Equilibria: An Appeal for a Consistent Thermodynamic Pedagogy Electronic Structures of Late versus Early Transition Metal Imido Complexes from 15N-NMR Signatures Total Synthesis of Tagitinins, Goyazensolide and Related Furanoheliangolides and their Covalent Interaction with Importin-5 (IPO5) Cover Picture: (Helv. Chim. Acta 10/2024)
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