Reactivity of Para‐Substituted Fluorobenzenes in Palladium‐catalyzed Intermolecular Direct Arylations

The influence of both electron‐withdrawing and electron‐donating substituents such as amino, bromo, chloro, ketone, methyl, methoxy, and nitro at C‐4 on fluorobenzene derivatives, for palladium‐catalyzed direct arylation at α‐position to the fluorine atom has been explored. With moderate electron‐withdrawing substituents, the reaction proceeds nicely using phosphine‐free PdCl2 catalyst, at a very low loading, and potassium pivalate/dimethylacetamide (PivOK/DMA) as catalytic system. In all cases, a regioselective arylation at the α position to the fluorine atom was observed. Moreover, a wide variety of substituents on the aryl bromide coupling partner, such as formyl, nitro, nitrile, chloro, and methyl, and also heteroaryl bromides was tolerated.

[1]  Jean‐François Soulé,et al.  Functionalization of C–H Bonds via Metal-Catalyzed Desulfitative Coupling: An Alternative Tool for Access to Aryl- or Alkyl-Substituted (Hetero)arenes , 2015 .

[2]  R. Cao,et al.  Palladium nanocrystals stabilized by cucurbit[6]uril as efficient heterogeneous catalyst for direct C–H functionalization of polyfluoroarenes , 2015 .

[3]  Jean‐François Soulé,et al.  Synthesis of (Poly)fluorobiphenyls through Metal‐catalyzed CH Bond Activation/Arylation of (Poly)fluorobenzene Derivatives , 2014 .

[4]  Tao Yan,et al.  Reactivity of 3‐Substituted Fluorobenzenes in Palladium‐ Catalysed Direct Arylations with Aryl Bromides , 2014 .

[5]  Lei Wang,et al.  Palladium‐Catalyzed Desulfitative Direct CH Arylation of Electron‐Deficient Polyfluoroarenes with Sodium Arenesulfinates , 2014 .

[6]  R. Rossi,et al.  Cross‐Coupling of Heteroarenes by CH Functionalization: Recent Progress towards Direct Arylation and Heteroarylation Reactions Involving Heteroarenes Containing One Heteroatom , 2014 .

[7]  Tao Yan,et al.  Influence of 1,3‐Difluorobenzene Substituents for Palladium‐Catalyzed Direct Arylations , 2013 .

[8]  Junxiang Zhang,et al.  Controllable direct arylation: fast route to symmetrical and unsymmetrical 4,7-diaryl-5,6-difluoro-2,1,3-benzothiadiazole derivatives for organic optoelectronic materials. , 2013, Journal of the American Chemical Society.

[9]  I. Larrosa,et al.  Arene-metal π-complexation as a traceless reactivity enhancer for C-H arylation. , 2013, Journal of the American Chemical Society.

[10]  A. Charette,et al.  C-H functionalization of cyclopropanes: a practical approach employing a picolinamide auxiliary. , 2013, Organic letters.

[11]  O. Miljanić,et al.  Superhydrophobic perfluorinated metal-organic frameworks. , 2013, Chemical communications.

[12]  Kuo‐Wei Huang,et al.  Preparation of fluorinated biaryls through direct palladium-catalyzed coupling of polyfluoroarenes with aryltrifluoroborates , 2013 .

[13]  Bao-hang Han,et al.  Fluorinated Porous Organic Polymers via Direct C-H Arylation Polycondensation. , 2013, ACS macro letters.

[14]  Frank Glorius,et al.  C-H bond activation enables the rapid construction and late-stage diversification of functional molecules. , 2013, Nature chemistry.

[15]  J. Yu,et al.  Direct C-arylation of polyfluoroarenes with diaryliodonium salts via Pd(OAc)2-catalysis , 2013 .

[16]  G. Aullón,et al.  Highly fluorescent complexes with gold, palladium or platinum linked to perylene through a tetrafluorophenyl group. , 2013, Dalton transactions.

[17]  Tao Yan,et al.  Synthesis of heteroarylated polyfluorobiphenyls via palladium-catalyzed sequential sp2 C-H bonds functionalizations. , 2013, The Journal of organic chemistry.

[18]  A. Jen,et al.  C–H activation: making diketopyrrolopyrrole derivatives easily accessible , 2013 .

[19]  F. Ozawa,et al.  A Highly Efficient Catalytic System for Polycondensation of 2,7-Dibromo-9,9-dioctylfluorene and 1,2,4,5-Tetrafluorobenzene via Direct Arylation , 2013 .

[20]  S. Gorelsky.  Origins of regioselectivity of the palladium-catalyzed (aromatic)CH bond metalation–deprotonation , 2013 .

[21]  J. A. May,et al.  A general method for the enantioselective synthesis of α-chiral heterocycles. , 2012, Organic letters.

[22]  X. Hou,et al.  Pd(OAc)2 catalyzed direct arylation of electron-deficient arenes without ligands or with monoprotected amino acid assistance. , 2012, Chemical communications.

[23]  C. So,et al.  Palladium-catalyzed direct arylation of polyfluoroarenes with aryl tosylates and mesylates , 2012 .

[24]  Junichiro Yamaguchi,et al.  Funktionalisierung von C‐H‐Bindungen: neue Synthesemethoden für Naturstoffe und Pharmazeutika , 2012 .

[25]  Junichiro Yamaguchi,et al.  C-H bond functionalization: emerging synthetic tools for natural products and pharmaceuticals. , 2012, Angewandte Chemie.

[26]  J. C. Bernhammer,et al.  Pyrazolin-5-ylidene Palladium(II) Complexes: Synthesis, Characterization, and Application in the Direct Arylation of Pentafluorobenzene , 2012 .

[27]  Wei Lu,et al.  Synthesis of π-Conjugated Polymers Containing Fluorinated Arylene Units via Direct Arylation: Efficient Synthetic Method of Materials for OLEDs , 2012 .

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

[29]  C. Chai,et al.  Scope of direct arylation of fluorinated aromatics with aryl sulfonates. , 2012, Organic & biomolecular chemistry.

[30]  Zhi Wang,et al.  Discovery of a full-color-tunable fluorescent core framework through direct C-H (hetero)arylation of N-heterocycles. , 2012, Chemistry.

[31]  H. Huynh,et al.  1,2,3-Triazolin-5-ylidenes: Synthesis of Hetero-bis(carbene) Pd(II) Complexes, Determination of Donor Strengths, and Catalysis , 2012 .

[32]  Jie Wu,et al.  Synthesis of 2-(polyfluoroaryl)benzofurans via a copper(I)-catalyzed reaction of 2-(2,2-dibromovinyl)phenol with polyfluoroarene. , 2012, Organic letters.

[33]  K. Laali,et al.  Pd(OAc)2-catalyzed cross-coupling of polyfluoroarenes with simple aromatics in imidazolium ionic liquids (ILs) without oxidant and additive and with recycling/reuse of the IL , 2011 .

[34]  I. Larrosa,et al.  Carboxylic acids as traceless directing groups for formal meta-selective direct arylation. , 2011, Angewandte Chemie.

[35]  O. Baudoin.  Transition metal-catalyzed arylation of unactivated C(sp3)-H bonds. , 2011, Chemical Society reviews.

[36]  O. Daugulis,et al.  A general method for copper-catalyzed arene cross-dimerization. , 2011, Journal of the American Chemical Society.

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

[38]  Zhenan Bao,et al.  Aryl-Perfluoroaryl Substituted Tetracene: Induction of Face-to-Face pi-pi Stacking and Enhancement of Charge Carrier Properties , 2011 .

[39]  T. Kanbara,et al.  Polycondensation of Dibromofluorene Analogues with Tetrafluorobenzene via Direct Arylation , 2011 .

[40]  David Lapointe,et al.  Predictable and site-selective functionalization of poly(hetero)arene compounds by palladium catalysis. , 2011, The Journal of organic chemistry.

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

[42]  M. Hong,et al.  Pd/PR3-catalyzed cross-coupling of aromatic carboxylic acids with electron-deficient polyfluoroarenes via combination of decarboxylation with sp2 C-H cleavage. , 2011, The Journal of organic chemistry.

[43]  L. Ackermann,et al.  Direct arylations of electron-deficient (hetero)arenes with aryl or alkenyl tosylates and mesylates. , 2011, Chemical communications.

[44]  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.

[45]  J. Mousseau,et al.  Umpolung direct arylation reactions: facile process requiring only catalytic palladium and substoichiometric amount of silver salts. , 2010, Journal of the American Chemical Society.

[46]  David Lapointe,et al.  Overview of the Mechanistic Work on the Concerted Metallation-Deprotonation Pathway , 2010 .

[47]  Olivier René,et al.  Room-temperature direct arylation of polyfluorinated arenes under biphasic conditions. , 2010, Organic letters.

[48]  Can-cheng Guo,et al.  Pd-catalyzed decarboxylative arylation of thiazole, benzoxazole, and polyfluorobenzene with substituted benzoic acids. , 2010, Organic letters.

[49]  L. Ackermann,et al.  Übergangsmetallkatalysierte direkte Arylierungen von (Hetero)Arenen durch C‐H‐Bindungsbruch , 2009 .

[50]  A. Kapdi,et al.  Transition-metal-catalyzed direct arylation of (hetero)arenes by C-H bond cleavage. , 2009, Angewandte Chemie.

[51]  H. Doucet,et al.  Regioselective C-2 or C-5 Direct Arylation of Pyrroles with Aryl Bromides using a Ligand-Free Palladium Catalyst , 2009 .

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

[53]  N. Tamaoki,et al.  Thin-film transistors based on liquid-crystalline tetrafluorophenylter thiophene derivatives: thin-film structure and carrier transport , 2009 .

[54]  L. Ackermann.  Modern arylation methods , 2009 .

[55]  Dongbing Zhao,et al.  Phosphine-free, palladium-catalyzed arylation of heterocycles through C-H bond activation with pivalic acid as a cocatalyst. , 2009, Chemistry.

[56]  D. Gryko,et al.  Energy- and Electron-Transfer Processes in Corrole−Perylenebisimide−Triphenylamine Array , 2008 .

[57]  A. Kimura,et al.  Meso-disubstituted anthracenes with fluorine-containing groups: synthesis, light-emitting characteristics, and photostability. , 2008, Organic letters.

[58]  Chung‐Chih Wu,et al.  Functionalized dibenzo[g,p]chrysenes: variable photophysical and electronic properties and liquid-crystal chemistry. , 2008, Organic letters.

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

[60]  O. Daugulis,et al.  Two methods for direct ortho-arylation of benzoic acids. , 2007, Journal of the American Chemical Society.

[61]  F. Maseras,et al.  Proton-abstraction mechanism in the palladium-catalyzed intramolecular arylation: substituent effects. , 2007, Journal of the American Chemical Society.

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

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

[64]  F. Maseras,et al.  Proton abstraction mechanism for the palladium-catalyzed intramolecular arylation. , 2006, Journal of the American Chemical Society.

[65]  Delano P. Chong,et al.  Estimation of Hammett sigma constants of substituted benzenes through accurate density-functional calculation of core-electron binding energy shifts , 2005 .

[66]  R. Chambers,et al.  Recent studies at Durham on direct fluorination , 1999 .

[67]  J. Hartwig,et al.  Palladium-Catalyzed Direct α-Arylation of Ketones. Rate Acceleration by Sterically Hindered Chelating Ligands and Reductive Elimination from a Transition Metal Enolate Complex , 1997 .

[68]  S. Buchwald,et al.  Palladium-Catalyzed α-Arylation of Ketones , 1997 .

[69]  S. Rozen.  Selective Fluorinations by Reagents Containing the OF Group. , 1996, Chemical reviews.

[70]  Corwin Hansch,et al.  A survey of Hammett substituent constants and resonance and field parameters , 1991 .