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DOI	10.1126/science.1222327
	Oxidative aliphatic C-H fluorination with fluoride ion catalyzed by a manganese porphyrin
	Liu W.; Huang X.; Cheng M.-J.; Nielsen R.J.; Goddard III W.A.; Groves J.T.
发表日期	2012
ISSN	0036-8075
起始页码	1322
结束页码	1325
卷号	337 期号:6100
英文摘要	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.
英文关键词	alkane; androstane derivative; benzene derivative; bornyl acetate; carbene; fluoride ion; manganese; porphyrin derivative; porphyrin manganese; steroid; terpenoid; unclassified drug; acetate; catalysis; fluoride; hydrocarbon; oxidation; salt; steroid; article; catalysis; fluorination; fluorine nuclear magnetic resonance; hydrogen bond; oxidation; priority journal; reaction time; stoichiometry; temperature
语种	英语
来源期刊	Science
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/244561
作者单位	Department of Chemistry, Frick Chemistry Laboratory, Princeton University, Princeton, NJ 08544, United States; Department of Chemistry, Materials and Process Simulation Center (MC 139-74), California Institute of Technology, Pasadena, CA 91125, United States
推荐引用方式 GB/T 7714	Liu W.,Huang X.,Cheng M.-J.,et al. Oxidative aliphatic C-H fluorination with fluoride ion catalyzed by a manganese porphyrin[J],2012,337(6100).
APA	Liu W.,Huang X.,Cheng M.-J.,Nielsen R.J.,Goddard III W.A.,&Groves J.T..(2012).Oxidative aliphatic C-H fluorination with fluoride ion catalyzed by a manganese porphyrin.Science,337(6100).
MLA	Liu W.,et al."Oxidative aliphatic C-H fluorination with fluoride ion catalyzed by a manganese porphyrin".Science 337.6100(2012).