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Oxidative Aliphatic C-H Fluorination with Fluoride Ion Catalyzed by a Manganese Porphyrin

Liu, Wei and Huang, Xiongyi and Cheng, Mu-Jeng and Nielsen, Robert J. and Goddard, William A., III and Groves, John T. (2012) Oxidative Aliphatic C-H Fluorination with Fluoride Ion Catalyzed by a Manganese Porphyrin. Science, 337 (6100). pp. 1322-1325. ISSN 0036-8075. https://resolver.caltech.edu/CaltechAUTHORS:20121127-142950090

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Abstract

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 5α-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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1126/science.1222327 DOIArticle
http://www.sciencemag.org/content/337/6100/1322PublisherArticle
ORCID:
AuthorORCID
Liu, Wei0000-0001-6249-3179
Huang, Xiongyi0000-0001-7156-8881
Cheng, Mu-Jeng0000-0002-8121-0485
Nielsen, Robert J.0000-0002-7962-0186
Goddard, William A., III0000-0003-0097-5716
Groves, John T.0000-0002-9944-5899
Additional Information:© 2012 American Association for the Advancement of Science. Received 23 March 2012; accepted 26 July 2012. We are grateful to NSF (grants CHE-0616633 and CHE-1148597 to J.T.G.) for support of this research. DFT calculations, hydrocarbon C-H activation, and the CalTech-Princeton collaboration were supported by the Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center, U.S. Department of Energy, Office of Science, Basic Energy Sciences, under award no. DE-SC0001298 to W.A.G. and J.T.G. A patent application has been filed through Princeton University on methods and catalysts presented in this paper. We thank S. Semproni for assistance with the x-ray crystal structure of MnIV(TMP)F2, data for which are available free of charge from the Cambridge Crystallographic Data Centre under reference no. CCDC 893742.
Funders:
Funding AgencyGrant Number
NSFCHE-0616633
NSFCHE-1148597
Department of Energy (DOE)DE-SC0001298
Issue or Number:6100
Record Number:CaltechAUTHORS:20121127-142950090
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20121127-142950090
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:35682
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:28 Nov 2012 15:40
Last Modified:03 Oct 2019 04:30

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