Rhodium-Catalyzed ortho-Selective C-F Bond Borylation of Polyfluoroarenes with Bpin-Bpin.

An ortho-selective C-F bond borylation between N-heterocycle-substituted polyfluoroarenes and Bpin-Bpin with simple and commercially available [Rh(cod)2 ]BF4 as a catalyst is now reported. The reaction proceeds under mild reaction conditions with high efficiency and broad substrate scope, even toward monofluoroarene, thus providing a facile access to a wide range of borylated fluoroarenes that are useful for photoelectronic materials. Preliminary mechanistic studies reveal that a Rh(III/V) catalytic cycle via a key intermediate rhodium(III) hydride complex [(H)Rh(III) Ln (Bpin)] may be involved in the reaction.

[1]  Sabrina I. Kalläne,et al.  C–H and C–F Bond Activations at a Rhodium(I) Boryl Complex: Reaction Steps for the Catalytic Borylation of Fluorinated Aromatics , 2015 .

[2]  Etsuko Tokunaga,et al.  Sterically Demanding Unsymmetrical Diaryl-λ3-iodanes for Electrophilic Pentafluorophenylation and an Approach to α-Pentafluorophenyl Carbonyl Compounds with an All-Carbon Stereocenter , 2014, ChemistryOpen.

[3]  Xingang Zhang,et al.  Palladium-catalyzed ortho-selective C-F activation of polyfluoroarenes with triethylsilane: a facile access to partially fluorinated aromatics. , 2013, Angewandte Chemie.

[4]  S. Cao,et al.  Noncatalytic pyridyl-directed alkylation and arylation carbon-fluorine bond of polyfluoroarenes with Grignard reagents. , 2013, The Journal of organic chemistry.

[5]  Q. Shen,et al.  Palladium-catalyzed coupling of polyfluorinated arenes with heteroarenes via C-F/C-H activation. , 2013, Organic letters.

[6]  Nihal Deligonul,et al.  Room-temperature synthesis of cyclometalated iridium(III) complexes: kinetic isomers and reactive functionalities , 2013 .

[7]  G. Haufe,et al.  C-F bond activation of unactivated aliphatic fluorides: synthesis of fluoromethyl-3,5-diaryl-2-oxazolidinones by desymmetrization of 2-aryl-1,3-difluoropropan-2-ols. , 2012, Angewandte Chemie.

[8]  Peter G. Jones,et al.  A New Framework of a Heteroleptic Iridium(III)–Carbene Complex as a Triplet Emitting Material , 2012 .

[9]  Q. Shen,et al.  Selective palladium-catalyzed C-F activation/carbon-carbon bond formation of polyfluoroaryl oxazolines. , 2012, The Journal of organic chemistry.

[10]  J. Yang,et al.  Pd-catalyzed direct cross-coupling of electron-deficient polyfluoroarenes with heteroaromatic tosylates. , 2011, Organic letters.

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

[12]  J. Love,et al.  Nickel-catalyzed selective defluorination to generate partially fluorinated biaryls. , 2011, Organic letters.

[13]  V. Grushin,et al.  Aromatic trifluoromethylation with metal complexes. , 2011, Chemical reviews.

[14]  R. Perutz,et al.  C-F and C-H bond activation of fluorobenzenes and fluoropyridines at transition metal centers: how fluorine tips the scales. , 2011, Accounts of chemical research.

[15]  J. Love,et al.  Cross coupling reactions of polyfluoroarenes via C-F activation. , 2010, Dalton transactions.

[16]  T. Braun,et al.  A highly reactive rhodium(I)-boryl complex as a useful tool for C-H bond activation and catalytic C-F bond borylation. , 2010, Angewandte Chemie.

[17]  J. Hartwig,et al.  C-H activation for the construction of C-B bonds. , 2010, Chemical reviews.

[18]  J. Hartwig,et al.  Origins of the selectivity for borylation of primary over secondary C-H bonds catalyzed by Cp*-rhodium complexes. , 2010, Journal of the American Chemical Society.

[19]  T. Jamison,et al.  Rhodium-catalyzed dehydrogenative borylation of cyclic alkenes. , 2010, Chemical communications.

[20]  G. Bernardinelli,et al.  Cyclometalated Iridium(III) Complexes as Photosensitizers for Long‐Range Electron Transfer: Occurrence of a Coulomb Barrier , 2009 .

[21]  H. Amii,et al.  C-F bond activation in organic synthesis. , 2009, Chemical reviews.

[22]  T. Braun,et al.  C-F activation at rhodium boryl complexes: formation of 2-fluoroalkyl-1,3,2-dioxaborolanes by catalytic functionalization of hexafluoropropene. , 2009, Angewandte Chemie.

[23]  T. Braun,et al.  Catalytic C-F activation and hydrodefluorination of fluoroalkyl groups. , 2009, Angewandte Chemie.

[24]  T. Braun,et al.  Katalytische C-F-Aktivierung und Hydrodefluorierung von Fluoralkylgruppen , 2009 .

[25]  M. Whittlesey,et al.  Catalytic hydrodefluorination of aromatic fluorocarbons by ruthenium N-heterocyclic carbene complexes. , 2009, Journal of the American Chemical Society.

[26]  S. Bernhard,et al.  Homogeneous catalytic system for photoinduced hydrogen production utilizing iridium and rhodium complexes. , 2008, Inorganic chemistry.

[27]  O. Ozerov,et al.  Hydrodefluorination of Perfluoroalkyl Groups Using Silylium-Carborane Catalysts , 2008, Science.

[28]  T. Braun,et al.  C-F activation of fluorinated arenes using NHC-stabilized nickel(0) complexes: selectivity and mechanistic investigations. , 2008, Journal of the American Chemical Society.

[29]  O. Daugulis,et al.  Copper-catalyzed arylation and alkenylation of polyfluoroarene C-H bonds. , 2008, Journal of the American Chemical Society.

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

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

[32]  R. Perutz,et al.  Sequential C-F activation and borylation of fluoropyridines via intermediate Rh(I) fluoropyridyl complexes: a multinuclear NMR investigation. , 2007, Chemical communications.

[33]  J. Fréchet,et al.  Organic semiconducting oligomers for use in thin film transistors. , 2007, Chemical reviews.

[34]  Roberta Ragni,et al.  Fluorinated organic materials for electronic and optoelectronic applications: the role of the fluorine atom. , 2007, Chemical communications.

[35]  C. Rowley,et al.  Catalytic intermolecular direct arylation of perfluorobenzenes. , 2006, Journal of the American Chemical Society.

[36]  Johannes W. Hofstraat,et al.  Blue emitting iridium complexes: synthesis, photophysics and phosphorescent devices , 2006 .

[37]  C. E. Webster,et al.  Rhodium boryl complexes in the catalytic, terminal functionalization of alkanes. , 2005, Journal of the American Chemical Society.

[38]  W. Jones.  Activation of C-F bonds using Cp*2ZrH2: a diversity of mechanisms , 2003 .

[39]  François Diederich,et al.  Wechselwirkungen mit aromatischen Ringen in chemischen und biologischen Erkennungsprozessen , 2003 .

[40]  F. Diederich,et al.  Interactions with aromatic rings in chemical and biological recognition. , 2003, Angewandte Chemie.

[41]  Hartwig,et al.  Thermal, catalytic, regiospecific functionalization of alkanes , 2000, Science.

[42]  V. Grushin,et al.  Catalytic C−F Bond Activation of Nonactivated Monofluoroarenes , 1999 .

[43]  M. Aizenberg,et al.  HOMOGENEOUS METAL-CATALYZED HYDROGENOLYSIS OF C-F BONDS , 1995 .

[44]  M. Aizenberg,et al.  Catalytic Activation of Carbon-Fluorine Bonds by a Soluble Transition Metal Complex , 1994, Science.

[45]  T. G. Richmond,et al.  Activation of Carbon-Fluorine Bonds by Metal Complexes , 1994 .

[46]  R. Perutz,et al.  Routes to fluorinated organic derivatives by nickel mediated C-F activation of heteroaromatics. , 2002, Chemical communications.