One‐pot synthesis of polyfluoroterphenyls via palladium‐catalyzed Suzuki–Miyaura coupling of chlorobromobenzene and CH bond functionalization of perfluoroarenes

An efficient tandem route for the synthesis of polyfluoroterphenyl derivatives has been developed. The target compounds were obtained in moderate to good yields by a Pd(OAc)2-catalyzed three-component coupling reaction involving palladium-catalyzed direct CH activation of perfluoroarenes. This in turn will set the stage for a wide application of this useful reaction for the synthesis of fluorinated liquid crystal compounds containing the privileged polyfluoroterphenyl structure. Copyright © 2014 John Wiley & Sons, Ltd.

[1]  Jianwei Xie,et al.  Palladium-catalyzed direct arylation of polyfluoroarene and facile synthesis of liquid crystal compounds , 2014 .

[2]  Jianwei Xie,et al.  A rapid and efficient catalysis system for the synthesis of 4‐vinylbiphenyl derivatives , 2013 .

[3]  Jianwei Xie,et al.  Metallomicelles of palladium(II) complexes as efficient catalysts for the Suzuki–Miyaura reaction in neat water , 2013 .

[4]  C. Bruneau,et al.  Ruthenium(II)-catalyzed C-H bond activation and functionalization. , 2012, Chemical reviews.

[5]  Xingang Zhang,et al.  Pd-catalyzed direct arylation of polyfluoroarenes on water under mild conditions using PPh3 ligand. , 2012, The Journal of organic chemistry.

[6]  C. Yeung,et al.  Catalytic dehydrogenative cross-coupling: forming carbon-carbon bonds by oxidizing two carbon-hydrogen bonds. , 2011, Chemical reviews.

[7]  Hu Li,et al.  Palladium-catalyzed cross-coupling of polyfluoroarenes with simple arenes. , 2011, Organic letters.

[8]  Ye Wei,et al.  Pd(OAc)(2)-catalyzed oxidative C-H/C-H cross-coupling of electron-deficient polyfluoroarenes with simple arenes. , 2010, Journal of the American Chemical Society.

[9]  J. Ellman,et al.  Rhodium-catalyzed C-C bond formation via heteroatom-directed C-H bond activation. , 2010, Chemical reviews.

[10]  Melanie S Sanford,et al.  Palladium-catalyzed ligand-directed C-H functionalization reactions. , 2010, Chemical reviews.

[11]  Xiujuan Feng,et al.  Salen and half-salen palladium(II) complexes: synthesis, characteriztion and catalytic activity toward Suzuki-Miyaura reaction , 2010 .

[12]  R. He,et al.  Bis(imino)pyridine palladium(II) complexes as efficient catalysts for the Suzuki–Miyaura reaction in water , 2009 .

[13]  jin-quan yu,et al.  Transition metal-catalyzed C-H activation reactions: diastereoselectivity and enantioselectivity. , 2009, Chemical Society reviews.

[14]  M. Hong,et al.  Palladium-catalyzed direct arylation of electron-deficient polyfluoroarenes with arylboronic acids. , 2009, Organic letters.

[15]  R. He,et al.  Bis(imino)pyridine palladium(II) complexes: Synthesis, structure and catalytic activity , 2009 .

[16]  R. He,et al.  Preparation and catalytic properties of bis(imino)pyridine palladium(II) complexes as efficient catalysts for Suzuki cross‐coupling reaction in water , 2009 .

[17]  O. Daugulis,et al.  A general method for copper-catalyzed arylation of arene C-H bonds. , 2008, Journal of the American Chemical Society.

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

[19]  Michael Hird,et al.  Fluorinated liquid crystals--properties and applications. , 2007, Chemical Society reviews.

[20]  K. K. Hii,et al.  A practical and general synthesis of unsymmetrical terphenyls. , 2007, The Journal of organic chemistry.

[21]  F. Felpin,et al.  Suzuki-Miyaura reactions of arenediazonium salts catalyzed by PD(0)/C. One-pot chemoselective double cross-coupling reactions. , 2007, Organic letters.

[22]  J. Vors,et al.  Flexible strategy for differentially 3,5-disubstituted 4-oxypyridin-2(1H)-ones based on site-selective Pd-catalyzed cross-coupling reactions. , 2007, Organic letters.

[23]  R. Pohl,et al.  Direct C-H arylation of purines: development of methodology and its use in regioselective synthesis of 2,6,8-trisubstituted purines. , 2006, Organic letters.

[24]  K. Fagnou,et al.  Mild and general conditions for the cross-coupling of aryl halides with pentafluorobenzene and other perfluoroaromatics. , 2006, Organic letters.

[25]  H. Shimizu,et al.  Negishi coupling strategy of a repetitive two-step method for oligoarene synthesis , 2006 .

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

[27]  Jikai Liu.  Natural terphenyls: developments since 1877. , 2006, Chemical reviews.

[28]  M. Recanatini,et al.  Identification of a terphenyl derivative that blocks the cell cycle in the G0-G1 phase and induces differentiation in leukemia cells. , 2006, Journal of medicinal chemistry.

[29]  Tobin J Marks,et al.  Fluorocarbon-modified organic semiconductors: molecular architecture, electronic, and crystal structure tuning of arene- versus fluoroarene-thiophene oligomer thin-film properties. , 2006, Journal of the American Chemical Society.

[30]  Ziqiang Guan,et al.  Highly substituted terphenyls as inhibitors of parasite cGMP-dependent protein kinase activity. , 2006, Journal of natural products.

[31]  T. Ema,et al.  Synthesis of a molecular tweezer containing pentafluorophenyl groups and investigation of the π-π stacking interaction for a pentafluorophenyl group in a polar organic solvent , 2005 .

[32]  G. Giannini,et al.  Studies on the apoptotic activity of natural and synthetic retinoids: discovery of a new class of synthetic terphenyls that potently support cell growth and inhibit apoptosis in neuronal and HL-60 cells. , 2005, Journal of medicinal chemistry.

[33]  C. Cho,et al.  Preparation of unsymmetrical terphenyls via the nickel-catalyzed cross-coupling of alkyl biphenylsulfonates with aryl Grignard reagents , 2004 .

[34]  M. Fakis,et al.  Luminescent poly(phenylene vinylene) derivatives with m‐terphenyl or 2,6‐diphenylpyridine kinked segments along the main chain: Synthesis, characterization, and stimulated emission , 2004 .

[35]  Detlef Pauluth,et al.  Advanced liquid crystals for television , 2004 .

[36]  I. Beletskaya,et al.  Successive Replacement of Halogen Atoms in 4,6-Dihaloquinolines in Cross-coupling Reactions with Arylboronic Acids Catalyzed by Palladium and Nickel Complexes , 2003 .

[37]  Tobin J Marks,et al.  Building blocks for n-type organic electronics: regiochemically modulated inversion of majority carrier sign in perfluoroarene-modified polythiophene semiconductors. , 2003, Angewandte Chemie.

[38]  S. Sebti,et al.  Design and synthesis of potent nonpeptidic farnesyltransferase inhibitors based on a terphenyl scaffold. , 2002, Journal of medicinal chemistry.

[39]  I. Sage,et al.  The synthesis and properties of host materials with fluoro substituents in the core and in a terminal chain for high dielectric biaxiality FLC mixtures , 2000 .

[40]  J. Goodby,et al.  The synthesis and mesomorphic properties of 4,4′′-dialkyl-2,2′,3- and 2,2′,3′-trifluoro-1,1′∶4′,1′′-terphenyls for high dielectric biaxiality ferroelectric liquid crystal mixtures , 2000 .

[41]  M. Hird,et al.  Synthesis and Physical Properties of a Novel Difluoroterphenyl Ferroelectric Liquid Crystal with a Fluorine at the Chiral Centre , 1999 .

[42]  J. Goodby,et al.  The synthesis and mesomorphic properties of 2,2′,3-tri- and 2,2′,3,3′-tetra-fluoro-1,1′∶4′,1″-terphenyls for high dielectric biaxiality ferroelectric liquid crystal mixtures , 1999 .

[43]  P. Knochel,et al.  Palladium-Catalyzed Cross-Coupling Reactions with Aryl Nonaflates: A Practical Alternative to Aryl Triflates. , 1998, The Journal of organic chemistry.

[44]  M. Hird,et al.  The synthesis of novel highly substituted benzene derivatives for use in palladium-catalysed cross-coupling reactions , 1998 .

[45]  Y. Shirota,et al.  Tri (p-terphenyl-4-yl) amine as a novel blue-emitting material for organic electroluminescent devices , 1997 .

[46]  G. W. Gray,et al.  The relationship between molecular structure and mesomorphic properties of 2,2′- and 3,2′-difluoroterphenyls synthesized by palladium-catalysed cross-couplings , 1995 .

[47]  A. J. Slaney,et al.  Synthesis and transition temperatures of host materials for ferroelectric mixtures , 1995 .

[48]  G. W. Gray,et al.  The synthesis and transition temperatures of some ferroelectric host materials based on 4- and 4′-(trans-4-alkylcyclohexylmethoxy)-2,3-difluorobiphenyls , 1994 .

[49]  A. J. Slaney,et al.  The synthesis and transition temperatures of some difluoro-substituted cyclohexanes , 1993 .

[50]  G. W. Gray,et al.  The synthesis and transition temperatures of some trans-4-alkylcyclohexylethyl-substituted 2,3-difluorobiphenyls , 1992 .

[51]  Michael Hird,et al.  The Synthesis of Several Lateral Difluoro-substituted 4,4″-Dialkyl- and 4,4″-Alkoxyalkyl-Terphenyls and a Rationalisation of the Effect of Such Substitution on Mesophase Type and Transition Temperatures , 1991 .

[52]  G. W. Gray,et al.  The Synthesis and Transition Temperatures of Some Lateral Monofluoro-substituted 4,4″- Dialkyl- and 4,4″-Alkoxyalkyl- 1, 1′: 4′,1″-terphenyls , 1991 .