Oxidative aliphatic C-H fluorination with fluoride ion catalyzed by a manganese porphyrin

Wei Liu, Xiongyi Huang, Mu Jeng Cheng, Robert J. Nielsen, William A. Goddard, John T. Groves

研究成果: Article

329 引文 斯高帕斯(Scopus)

摘要

Despite the growing importance of fluorinated organic compounds in drug development, there are no direct protocols for the fluorination of aliphatic C-H bonds using conveniently handled fluoride salts. We have discovered that a manganese porphyrin complex catalyzes alkyl fluorination by fluoride ion under mild conditions in conjunction with stoichiometric oxidation by iodosylbenzene. Simple alkanes, terpenoids, and even steroids were selectively fluorinated at otherwise inaccessible sites in 50 to 60% yield. Decalin was fluorinated predominantly at the C2 and C3 methylene positions. Bornyl acetate was converted to exo-5-fluoro-bornyl acetate, and 5a-androstan-17-one was fluorinated selectively in the A ring. Mechanistic analysis suggests that the regioselectivity for C-H bond cleavage is directed by an oxomanganese(V) catalytic intermediate followed by F delivery via an unusual manganese(IV) fluoride that has been isolated and structurally characterized.

原文English
頁(從 - 到)1322-1325
頁數4
期刊Science
337
發行號6100
DOIs
出版狀態Published - 2012 九月 14

All Science Journal Classification (ASJC) codes

  • General

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    Liu, W., Huang, X., Cheng, M. J., Nielsen, R. J., Goddard, W. A., & Groves, J. T. (2012). Oxidative aliphatic C-H fluorination with fluoride ion catalyzed by a manganese porphyrin. Science, 337(6100), 1322-1325. https://doi.org/10.1126/science.1222327