LiHMDS-Promoted Palladium-Catalyzed Sonogashira Cross-Coupling of Aryl Fluorides with Terminal Alkynes.

A highly efficient Pd-catalyzed Sonogashira coupling of various aryl fluorides with terminal alkynes in the presence of LiHMDS was developed. Both unreactive electron-rich fluoroarenes and electron-poor fluoroarenes proceeded smoothly and afforded the corresponding internal alkynes in moderate to excellent yields.

[1]  I. Özdemir,et al.  PEPPSI-Pd-NHC catalyzed Suzuki-Miyaura cross-coupling reactions in aqueous media , 2019, Tetrahedron.

[2]  Xiangrong Liu,et al.  Base-Mediated Defluorosilylation of C(sp2 )-F and C(sp3 )-F Bonds. , 2019, Angewandte Chemie.

[3]  A. Studer,et al.  Silyldefluorination of Fluoroarenes by Concerted Nucleophilic Aromatic Substitution. , 2018, Angewandte Chemie.

[4]  K. Fuchibe,et al.  Transition-Metal-Mediated and -Catalyzed C-F Bond Activation by Fluorine Elimination. , 2018, Angewandte Chemie.

[5]  R. McDonald,et al.  Alkene Isomerization–Hydroboration Catalyzed by First-Row Transition-Metal (Mn, Fe, Co, and Ni) N-Phosphinoamidinate Complexes: Origin of Reactivity and Selectivity , 2018, ACS Catalysis.

[6]  S. Cao,et al.  LiHMDS-Promoted Palladium or Iron-Catalyzed ipso-Defluoroborylation of Aryl Fluorides. , 2018, Organic letters.

[7]  N. Jux,et al.  Oxa[7]superhelicene: A π-Extended Helical Chromophore Based on Hexa-peri-hexabenzocoronenes. , 2018, Angewandte Chemie.

[8]  Xiaofeng Zhang,et al.  Pd-Catalyzed Decarboxylative Sonogashira Reaction via Decarboxylative Bromination. , 2018, Organic Letters.

[9]  Shuyan Yu,et al.  Ferrocenyl bisoxazoline as an efficient non‐phosphorus ligand for palladium‐catalyzed copper‐free Sonogashira reaction in aqueous solution , 2018 .

[10]  Wenyi Chu,et al.  Visible‐Light‐Assisted Cobalt‐2‐(hydroxyimino)‐1‐phenylpropan‐1‐one Complex Catalyzed Pd/Cu‐Free Sonogashira–Hagihara Cross‐Coupling Reaction , 2018 .

[11]  William Clegg,et al.  Utilising Sodium-Mediated Ferration for Regioselective Functionalisation of Fluoroarenes via C-H and C-F Bond Activations. , 2018, Angewandte Chemie.

[12]  H. Küçükbay,et al.  Efficient and green catalytic system incorporating new benzimidazolium salts for the Sonogashira cross‐coupling reaction , 2018 .

[13]  Cheng‐Pan Zhang,et al.  Sonogashira Reaction Using Arylsulfonium Salts as Cross-Coupling Partners. , 2017, Organic letters.

[14]  T. Hosoya,et al.  Copper-Catalyzed ipso-Borylation of Fluoroarenes , 2017 .

[15]  Mark R. Crimmin,et al.  Functionalisation of Carbon–Fluorine Bonds with Main Group Reagents , 2016, Synthesis.

[16]  U. Bora,et al.  A green protocol for ligand, copper and base free Sonogashira cross-coupling reaction , 2016 .

[17]  Mingyan Ye,et al.  Sonogashira coupling catalyzed by the Cu(Xantphos)I–Pd(OAc)2 system , 2016 .

[18]  Yangen Huang,et al.  Review of recent advances in CF bond activation of aliphatic fluorides , 2015 .

[19]  Xiangrong Liu,et al.  Ni-Catalyzed Borylation of Aryl Fluorides via C-F Cleavage. , 2015, Journal of the American Chemical Society.

[20]  T. Braun,et al.  Functionalization of fluorinated molecules by transition-metal-mediated C-F bond activation to access fluorinated building blocks. , 2015, Chemical reviews.

[21]  J. Weaver,et al.  C–F activation and functionalization of perfluoro- and polyfluoroarenes , 2014 .

[22]  S. Cao,et al.  Nickel-catalyzed N-heterocycle-directed cross-coupling of fluorinated arenes with organozinc reagents , 2014 .

[23]  Fengxiang Zhu,et al.  Nickel-catalyzed cross-coupling of aryl fluorides and organozinc reagents. , 2014, The Journal of organic chemistry.

[24]  P. Carroll,et al.  NiXantphos: A Deprotonatable Ligand for Room-Temperature Palladium-Catalyzed Cross-Couplings of Aryl Chlorides , 2014, Journal of the American Chemical Society.

[25]  J. Love,et al.  Nickel-catalyzed Csp2-Csp3 bond formation by carbon-fluorine activation. , 2014, Chemistry.

[26]  M. Ohashi,et al.  Palladium-catalyzed coupling reaction of perfluoroarenes with diarylzinc compounds. , 2014, Chemistry.

[27]  Lei Liu,et al.  Nickel-catalyzed sonogashira reactions of non-activated secondary alkyl bromides and iodides. , 2013, Angewandte Chemie.

[28]  S. Cao,et al.  Transition-metal-free Sonogashira-type cross-coupling of alkynes with fluoroarenes. , 2013, Organic letters.

[29]  G. Nelles,et al.  Pd-catalyzed sp2–sp cross-coupling reactions involving C–F bond activation in highly fluorinated nitrobenzene systems , 2013 .

[30]  Wangjun Guo,et al.  Cross-coupling of ArX with ArMgBr catalyzed by N-heterocyclic carbene-based nickel complexes. , 2013, The Journal of organic chemistry.

[31]  S. Ito,et al.  Umpolung of fluoroform by C-F bond activation: direct difluoromethylation of lithium enolates. , 2012, Angewandte Chemie.

[32]  Shao-Wei Huang,et al.  Synthesis and antifungal activity of novel sclerotiorin analogues. , 2012, Journal of agricultural and food chemistry.

[33]  N. Chatani,et al.  Nickel-catalyzed Suzuki-Miyaura reaction of aryl fluorides. , 2011, Journal of the American Chemical Society.

[34]  C. Nájera,et al.  Recent advances in Sonogashira reactions. , 2011, Chemical Society reviews.

[35]  T. Truong,et al.  Transition-metal-free alkynylation of aryl chlorides. , 2011, Organic letters.

[36]  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.

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

[38]  M. Pal Palladium-Catalyzed Alkynylationof Aryl and Hetaryl Halides: A Journey from Conventional PalladiumComplexes or Salts to Palladium/Carbon , 2009 .

[39]  M. Heravi,et al.  Recent Advances in the Application of the Sonogashira Method in the Synthesis of Heterocyclic Compounds , 2009 .

[40]  Xile Hu,et al.  Ni-catalyzed Sonogashira coupling of nonactivated alkyl halides: orthogonal functionalization of alkyl iodides, bromides, and chlorides. , 2009, Journal of the American Chemical Society.

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

[42]  K. Manabe,et al.  Synthesis of Substituted Monohalobenzenes via Ortho-Selective Cross-Coupling of Dihalobenzenes with Electron-Donating Ortho-Directing Groups , 2008 .

[43]  I. Fairlamb pi-Acidic alkene ligand effects in Pd-catalysed cross-coupling processes: exploiting the interaction of dibenzylidene acetone (dba) and related ligands with Pd(0) and Pd(II). , 2008, Organic & biomolecular chemistry.

[44]  K. Manabe,et al.  Ortho-SelectiveCross-Coupling of Fluorobenzenes with Grignard Reagents: Accelerationby Electron-Donating Ortho-DirectingGroups , 2008 .

[45]  P. Ghosh,et al.  Highly convenient amine-free sonogashira coupling in air in a polar mixed aqueous medium by trans- and cis-[(NHC)2PdX2] (X=Cl, Br) complexes of N/O-functionalized N-heterocyclic carbenes. , 2008, Chemistry.

[46]  C. Yoakim,et al.  Efficient nucleophilic aromatic substitution between aryl nitrofluorides and alkynes. , 2007, Organic letters.

[47]  C. Nájera,et al.  The Sonogashira reaction: a booming methodology in synthetic organic chemistry. , 2007, Chemical reviews.

[48]  Jean‐Cyrille Hierso,et al.  Palladium-based catalytic systems for the synthesis of conjugated enynes by sonogashira reactions and related alkynylations. , 2007, Angewandte Chemie.

[49]  A. Jutand,et al.  Mechanism of the copper-free palladium-catalyzed Sonagashira reactions: multiple role of amines. , 2007, Chemistry.

[50]  T. Schaub,et al.  Catalytic C-C bond formation accomplished by selective C-F activation of perfluorinated arenes. , 2006, Journal of the American Chemical Society.

[51]  A. Kapdi,et al.  Influence of the dba Substitution on the Reactivity of Palladium(0) Complexes Generated from Pd02(dba-n,n‘-Z)3 or Pd0(dba-n,n‘-Z)2 and PPh3 in Oxidative Addition with Iodobenzene , 2006 .

[52]  J. Ruiz,et al.  Suzuki cross-coupling reaction of fluorobenzene with heterogeneous palladium catalysts , 2006 .

[53]  E. Nakamura,et al.  Nickel-catalyzed cross-coupling reaction of aryl fluorides and chlorides with grignard reagents under nickel/magnesium bimetallic cooperation. , 2005, Journal of the American Chemical Society.

[54]  D. Prajapati,et al.  A Novel Indium-Catalyzed Sonogashira Coupling Reaction, Effected in the Absence of a Copper Salt, Phosphine Ligand and Palladium , 2005 .

[55]  K. Tamao,et al.  Nickel- and palladium-catalyzed cross-coupling reaction of polyfluorinated arenes and alkenes with grignard reagents , 2005 .

[56]  Y. Kondo,et al.  Catalytic Activation of Silylated Nucleophiles Using tBu‐P4 as a Base , 2005 .

[57]  J. Dankwardt Transition metal catalyzed cross-coupling of aryl Grignard reagents with aryl fluorides via Pd- or Ni-activation of the C–F bond: an efficient synthesis of unsymmetrical biaryls – application of microwave technology in ligand and catalyst screening , 2005 .

[58]  A. Kapdi,et al.  Eta2-dba complexes of Pd(0): the substituent effect in Suzuki-Miyaura coupling. , 2004, Organic letters.

[59]  G. C. Fu,et al.  The first applications of carbene ligands in cross-couplings of alkyl electrophiles: sonogashira reactions of unactivated alkyl bromides and iodides. , 2003, Journal of the American Chemical Society.

[60]  H. Plenio,et al.  A versatile catalyst for the Sonogashira coupling of aryl chlorides. , 2003, Angewandte Chemie.

[61]  Shu Yu,et al.  Palladium(0)-catalyzed amination, Stille coupling, and Suzuki coupling of electron-deficient aryl fluorides. , 2003, Journal of the American Chemical Society.

[62]  H. Rzepa,et al.  A computational study of the mechanism of palladium insertion into alkynyl and aryl carbon–fluorine bonds , 2002 .

[63]  S. Buchwald,et al.  Pd(PhCN)(2)Cl(2)/P(t-Bu)(3): a versatile catalyst for Sonogashira reactions of aryl bromides at room temperature. , 2000, Organic letters.

[64]  R. Perutz,et al.  Inertness of the Aryl−F Bond toward Oxidative Addition to Osmium and Rhodium Complexes: Thermodynamic or Kinetic Origin? , 1998 .

[65]  C. Amatore,et al.  Identification of the Effective Palladium(0) Catalytic Species Generated in Situ from Mixtures of Pd(dba)2 and Bidentate Phosphine Ligands. Determination of Their Rates and Mechanism in Oxidative Addition , 1997 .

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

[67]  P. Power,et al.  Three-coordinate iron complexes: x-ray structural characterization of the iron amide-bridged dimers [Fe(NR2)2]2 (R = SiMe3, C6H5) and the adduct Fe[N(SiMe3)2]2(THF) and determination of the association energy of the monomer Fe{N(SiMe3)2}2 in solution , 1991 .

[68]  P. Power,et al.  Mononuclear cobalt(II) complexes having alkoxide and amide ligands: synthesis and x-ray crystal structures of [Co(Cl)(OC-tert-Bu3)2.Li(THF)3], [Li(THF)4.5][Co{N(SiMe3)2}(OC-tert-Bu3)2], and [Li{Co(N(SiMe3)2)(OC-tert-Bu3)2}] , 1986 .