Manganese-catalyzed oxidative benzylic C-H fluorination by fluoride ions.

An efficient protocol for the selective fluorination of benzylic C-H bonds is described. The process is catalyzed by manganese salen complexes and uses nucleophilic fluorine sources, such as triethylamine trihydrofluoride and KF. Reaction rates are sufficiently high (30 min) to allow adoption for the incorporation of (18)F fluoride sources for PET imaging applications.

[1]  David C. Miller,et al.  A polycomponent metal-catalyzed aliphatic, allylic, and benzylic fluorination. , 2012, Angewandte Chemie.

[2]  Jimmy Wu,et al.  Palladium-catalyzed allylic fluorination of cinnamyl phosphorothioate esters. , 2012, Organic letters.

[3]  William A. Goddard,et al.  Oxidative Aliphatic C-H Fluorination with Fluoride Ion Catalyzed by a Manganese Porphyrin , 2012, Science.

[4]  M. Sanford,et al.  Pd-catalyzed C-H fluorination with nucleophilic fluoride. , 2012, Organic letters.

[5]  J. Hartwig,et al.  Copper-mediated fluorination of aryl iodides. , 2012, Journal of the American Chemical Society.

[6]  S. Inagi,et al.  Electrochemical fluorination using alkali-metal fluorides. , 2012, Angewandte Chemie.

[7]  V. Gouverneur,et al.  Transition metal catalysis and nucleophilic fluorination. , 2012, Chemical communications.

[8]  Pierre Kennepohl,et al.  Fluorine transfer to alkyl radicals. , 2012, Journal of the American Chemical Society.

[9]  V. Gouverneur Radiochemistry: Flipping fluoride's reactivity. , 2012, Nature chemistry.

[10]  Eunsung Lee,et al.  A Fluoride-Derived Electrophilic Late-Stage Fluorination Reagent for PET Imaging , 2011, Science.

[11]  A. Doyle,et al.  Palladium-catalyzed regio- and enantioselective fluorination of acyclic allylic halides. , 2011, Journal of the American Chemical Society.

[12]  Timothy Noël,et al.  Accelerating palladium-catalyzed C-F bond formation: use of a microflow packed-bed reactor. , 2011, Angewandte Chemie.

[13]  T. Ritter,et al.  Catalysis for fluorination and trifluoromethylation , 2011, Nature.

[14]  A. Gee,et al.  Palladium-catalyzed allylic fluorination. , 2011, Angewandte Chemie.

[15]  J. Conrad,et al.  Enantioselective organocatalytic α-fluorination of cyclic ketones. , 2011, Journal of the American Chemical Society.

[16]  A. Doyle,et al.  Palladium-catalyzed asymmetric synthesis of allylic fluorides. , 2010, Journal of the American Chemical Society.

[17]  T. Ritter,et al.  Silver-catalyzed late-stage fluorination. , 2010, Journal of the American Chemical Society.

[18]  J. Kalow,et al.  Enantioselective ring opening of epoxides by fluoride anion promoted by a cooperative dual-catalyst system. , 2010, Journal of the American Chemical Society.

[19]  V. Grushin The organometallic fluorine chemistry of palladium and rhodium: studies toward aromatic fluorination. , 2010, Accounts of chemical research.

[20]  Steven V. Ley,et al.  Development of fluorination methods using continuous-flow microreactors , 2009 .

[21]  S. Buchwald,et al.  Formation of ArF from LPdAr(F): Catalytic Conversion of Aryl Triflates to Aryl Fluorides , 2009, Science.

[22]  T. Mei,et al.  Versatile Pd(OTf)2 x 2 H2O-catalyzed ortho-fluorination using NMP as a promoter. , 2009, Journal of the American Chemical Society.

[23]  T. Ritter,et al.  Silver-mediated fluorination of functionalized aryl stannanes. , 2009, Journal of the American Chemical Society.

[24]  Frances H Arnold,et al.  Chemo-enzymatic fluorination of unactivated organic compounds. , 2009, Nature chemical biology.

[25]  Tobias Ritter,et al.  Palladiumvermittelte Fluorierung von Arylboronsäuren , 2008 .

[26]  T. Ritter,et al.  Palladium-mediated fluorination of arylboronic acids. , 2008, Angewandte Chemie.

[27]  F. Cavani,et al.  Direct Oxyfluorination of Hydrocarbons on Metal Fluorides , 2008 .

[28]  Pius August Schubiger,et al.  Molecular imaging with PET. , 2008, Chemical reviews.

[29]  K. Kirk Fluorination in Medicinal Chemistry: Methods, Strategies, and Recent Developments , 2008 .

[30]  David O'Hagan,et al.  Understanding organofluorine chemistry. An introduction to the C-F bond. , 2008, Chemical Society reviews.

[31]  S. Purser,et al.  Fluorine in medicinal chemistry. , 2008, Chemical Society reviews.

[32]  F. Diederich,et al.  Fluorine in Pharmaceuticals: Looking Beyond Intuition , 2007, Science.

[33]  Mohammed Salah Ibrahim,et al.  Trans-dioxo manganese(V) porphyrins. , 2007, Journal of the American Chemical Society.

[34]  G. Sandford Elemental fluorine in organic chemistry (1997–2006) , 2007 .

[35]  M. Sanford,et al.  Palladium-catalyzed fluorination of carbon-hydrogen bonds. , 2006, Journal of the American Chemical Society.

[36]  S. Rozen Elemental Fluorine and HOF·CH3CN in Service of General Organic Chemistry , 2005 .

[37]  J. Patterson,et al.  How Available is Positron Emission Tomography in the United States? , 2005, Molecular Imaging and Biology.

[38]  Q. Guo,et al.  Quantum-chemical predictions of absolute standard redox potentials of diverse organic molecules and free radicals in acetonitrile. , 2005, Journal of the American Chemical Society.

[39]  Haoran Sun,et al.  Anhydrous tetrabutylammonium fluoride. , 2005, Journal of the American Chemical Society.

[40]  P. Jeschke The Unique Role of Fluorine in the Design of Active Ingredients for Modern Crop Protection , 2004, Chembiochem : a European journal of chemical biology.

[41]  Martin Stahl,et al.  Fluorine in Medicinal Chemistry , 2004, Chembiochem : a European journal of chemical biology.

[42]  D. Schlyer,et al.  PET tracers and radiochemistry. , 2004, Annals of the Academy of Medicine, Singapore.

[43]  T. Fuchigami,et al.  Anodic benzylic fluorination of toluene, ethylbenzene, and cumene derivatives , 2002 .

[44]  B. Smart Fluorine substituent effects (on bioactivity) , 2001 .

[45]  T. Katsuki,et al.  Highly enantioselective benzylic hydroxylation with concave type of (salen)manganese(III) complex , 1998 .

[46]  J. Groves,et al.  Detection and Characterization of an Oxomanganese(V) Porphyrin Complex by Rapid-Mixing Stopped-Flow Spectrophotometry , 1997 .

[47]  A. Wolf,et al.  Working Against Time: Rapid Radiotracer Synthesis and Imaging the Human Brain , 1997 .

[48]  Wei Zhang,et al.  Highly enantioselective epoxidation catalysts derived from 1,2-diaminocyclohexane , 1991 .

[49]  Scott R. Wilson,et al.  Enantioselective Epoxidation of Unfunctionalized Olefins Catalyzed by (salen)Manganese Complexes , 1990 .

[50]  D. Barton,et al.  Fluorination at saturated carbon. 1. Direct substitution of adamantanes , 1976 .

[51]  J. B. Wilford,et al.  The fluorination of methane and related compounds by copper(II) fluoride and other metal fluorides , 1975 .

[52]  W. Middleton New fluorinating reagents. Dialkylaminosulfur fluorides , 1975 .

[53]  W. Miller,et al.  The Mechanism of Fluorination. I. Fluorine Sensitized Oxidation of Trichloro- and Tetrachloroethylene , 1956 .