Pyridine-promoted dediazoniation of aryldiazonium tetrafluoroborates: Application to the synthesis of SF5-substituted phenylboronic esters and iodobenzenes

Summary Pyridine promotes dediazoniation of aryldiazonium tetrafluoroborates. The formed aryl radicals were trapped with B2pin2, iodine, or tetrahydrofuran to afford boronic esters, iodobenzenes and benzenes, respectively. The application to the synthesis of (pentafluorosulfanyl)phenylboronic esters, iodo(pentafluorosulfanyl)benzenes and (pentafluorosulfanyl)benzene is shown.

[1]  J. Welch,et al.  Preparation and utility of organic pentafluorosulfanyl-containing compounds. , 2015, Chemical reviews.

[2]  G. Szulczewski,et al.  Pentafluorosulfanylbenzene chemistry: Role of copper in the Sheppard reaction, direct fluorination of aromatic sulfenyl chlorides, and several potentially energetic SF5-benzenes , 2014 .

[3]  K. Laali,et al.  The 2,4-dimethyl-7-pentafluorosulfanyl-5-(trifluoromethyl)dibenzo[b,d]thiophenium trifluoromethanesulfonate: The SF5-analog of Umemoto salt , 2014 .

[4]  P. Beier,et al.  Synthesis of aliphatic sulfur pentafluorides by oxidation of SF₅-containing anisole, phenols, and anilines. , 2014, The Journal of organic chemistry.

[5]  Jianliang Xiao,et al.  Methanol-Promoted Borylation of Arylamines: A Simple and Green Synthetic Method to Arylboronic Acids and Arylboronates , 2014, Synlett.

[6]  W. Erb,et al.  An easy route to (hetero)arylboronic acids. , 2014, Chemistry.

[7]  M. Zanda,et al.  The pentafluorosulfanyl group in cannabinoid receptor ligands: synthesis and comparison with trifluoromethyl and tert-butyl analogues , 2014 .

[8]  Etsuko Tokunaga,et al.  Bis(pentafluorosulfanyl)phenyl Azide as an Expeditious Tool for Click Chemistry toward Antitumor Pharmaceuticals , 2014, ChemMedChem.

[9]  K. Laali,et al.  4‐(Pentafluorosulfanyl)benzenediazonium Tetrafluoroborate: A Versatile Launch Pad for the Synthesis of Aromatic SF5 Compounds via Cross Coupling, Azo Coupling, Homocoupling, Dediazoniation, and Click Chemistry , 2014 .

[10]  Shane W. Krska,et al.  A traceless directing group for C-H borylation. , 2013, Angewandte Chemie.

[11]  W. Chui,et al.  Fragment-based approach to the design of 5-chlorouracil-linked-pyrazolo[1,5-a][1,3,5]triazines as thymidine phosphorylase inhibitors. , 2013, European journal of medicinal chemistry.

[12]  E. Carreira,et al.  Ir-catalyzed preparation of SF5-substituted potassium aryl trifluoroborates via C-H borylation and their application in the Suzuki-Miyaura reaction. , 2013, Organic letters.

[13]  Yan‐Bo Yu,et al.  Pd-catalyzed direct arylation of nitro(pentafluorosulfanyl)benzenes with aryl bromides. , 2013, Organic letters.

[14]  M. Vaultier,et al.  Iron‐Catalysed Borylation of Arenediazonium Salts to Give Access to Arylboron Derivatives via Aryl(amino)boranes at Room Temperature , 2013 .

[15]  P. Beier,et al.  Synthesis of Pentafluorosulfanyl-Containing Indoles and Oxindoles , 2013 .

[16]  J. Wang,et al.  Synthesis of pinacol arylboronates from aromatic amines: a metal-free transformation. , 2013, The Journal of organic chemistry.

[17]  M. Zanda,et al.  Synthetic chemistry and biological activity of pentafluorosulphanyl (SF5) organic molecules , 2012 .

[18]  P. Beier,et al.  Oxidative Nucleophilic Substitution of Hydrogen in Nitro(pentafluorosulfanyl)benzenes with Alkyl Grignard and Lithium Reagents. , 2012 .

[19]  Etsuko Tokunaga,et al.  3,5-Bis(pentafluorosulfanyl)phenylboronic acid: A new organocatalyst for Conia-ene carbocyclization of 1,3-dicarbonyl compounds having terminal alkynes , 2012 .

[20]  B. List,et al.  Deracemization of α-aryl hydrocoumarins via catalytic asymmetric protonation of ketene dithioacetals. , 2012, Journal of the American Chemical Society.

[21]  Jian Yu,et al.  Metal‐Free, Visible Light‐Induced Borylation of Aryldiazonium Salts: A Simple and Green Synthetic Route to Arylboronates , 2012 .

[22]  A. Slawin,et al.  Allosteric agonists of the calcium receptor (CaR): fluorine and SF5 analogues of cinacalcet. , 2012, Organic & biomolecular chemistry.

[23]  P. Knochel,et al.  Preparations and reactions of SF5-substituted aryl and heteroaryl derivatives via Mg and Zn organometallics. , 2012, Chemistry.

[24]  M. Ingleson A Perspective on Direct Electrophilic Arene Borylation , 2012 .

[25]  オリヴィエール・ブイジーン,et al.  Process for the preparation of fluorinated organic compounds , 2012 .

[26]  Haitao Yu,et al.  Sandmeyer-Type Reaction to Pinacol Arylboronates in Water Phase: A Green Borylation Process , 2012, Synlett : Accounts and Rapid Communications in Synthetic Organic Chemistry.

[27]  A. Prokofjevs,et al.  Cationic tricoordinate boron intermediates: borenium chemistry from the organic perspective. , 2012, Chemical reviews.

[28]  R. Pohl,et al.  Direct Amination of Nitro(pentafluorosulfanyl)benzenes through Vicarious Nucleophilic Substitution of Hydrogen , 2012 .

[29]  Lloyd M Garrick,et al.  Discovery of practical production processes for arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides): Beginning of a new era of “super-trifluoromethyl” arene chemistry and its industry , 2012, Beilstein journal of organic chemistry.

[30]  J. Hartwig,et al.  On the interpretation of deuterium kinetic isotope effects in C-H bond functionalizations by transition-metal complexes. , 2012, Angewandte Chemie.

[31]  N. Takada,et al.  Crystal Structures and Triboluminescence Based on Trifluoromethyl and Pentafluorosulfanyl Substituted Asymmetric N-Phenyl Imide Compounds , 2012 .

[32]  jin-quan yu,et al.  Pd-catalyzed oxidative ortho-C-H borylation of arenes. , 2012, Journal of the American Chemical Society.

[33]  E. Álvarez,et al.  Use of hemilabile N,N ligands in nitrogen-directed iridium-catalyzed borylations of arenes. , 2011, Angewandte Chemie.

[34]  M. Ingleson,et al.  Simple inexpensive boron electrophiles for direct arene borylation. , 2011, Chemical communications.

[35]  H. Ohmiya,et al.  Rh-catalyzed ortho-selective C-H borylation of N-functionalized arenes with silica-supported bridgehead monophosphine ligands. , 2011, Journal of the American Chemical Society.

[36]  P. Beier,et al.  Hydroxylation of nitro-(pentafluorosulfanyl)benzenes via vicarious nucleophilic substitution of hydrogen , 2011 .

[37]  T. Zevaco,et al.  Solid phase synthesis of selectively deuterated arenes. , 2011, Chemical communications.

[38]  W. R. Dolbier,et al.  Use of 1,3-dipolar reactions for the preparation of SF5-substituted five-membered ring heterocycles. Pyrroles and thiophenes , 2011 .

[39]  P. Beier,et al.  Preparation of SF5 aromatics by vicarious nucleophilic substitution reactions of nitro(pentafluorosulfanyl)benzenes with carbanions. , 2011, The Journal of organic chemistry.

[40]  M. Ingleson,et al.  Pinacol boronates by direct arene borylation with borenium cations. , 2011, Angewandte Chemie.

[41]  P. Beier,et al.  S(N)Ar reactions of nitro-(pentafluorosulfanyl)benzenes to generate SF5 aryl ethers and sulfides. , 2011, Organic letters.

[42]  J. Wang,et al.  Direct conversion of arylamines to pinacol boronates: a metal-free borylation process. , 2010, Angewandte Chemie.

[43]  W. R. Dolbier,et al.  Preparation of pentafluorosulfanyl (SF5) pyrrole carboxylic acid esters. , 2009, The Journal of organic chemistry.

[44]  Li Dang,et al.  A facile route to aryl boronates: room-temperature, copper-catalyzed borylation of aryl halides with alkoxy diboron reagents. , 2009, Angewandte Chemie.

[45]  F. Diederich,et al.  Pentafluorosulfanyl as a Novel Building Block for Enzyme Inhibitors: Trypanothione Reductase Inhibition and Antiprotozoal Activities of Diarylamines , 2009, Chembiochem : a European journal of chemical biology.

[46]  I. Davies,et al.  A Practical Synthesis of α-Aryl Methyl Ketones via a Transition-Metal-Free Meerwein Arylation , 2007 .

[47]  W. R. Dolbier,et al.  A convenient and efficient method for incorporation of pentafluorosulfanyl (SF5) substituents into aliphatic compounds , 2006 .

[48]  Wei Zhu,et al.  Formation of arylboronates by a CuI-catalyzed coupling reaction of pinacolborane with aryl iodides at room temperature , 2006 .

[49]  D. Hall Boronic acids : preparation and applications in organic synthesis and medicine , 2005 .

[50]  D. Grainger,et al.  Self-Assembled Organic Monolayers Terminated in Perfluoroalkyl Pentafluoro-λ6-sulfanyl (-SF5) Chemistry on Gold , 2004 .

[51]  W. R. Dolbier,et al.  A new synthesis of pentafluorosulfanylbenzene. , 2004, Organic Letters.

[52]  G. Mitchell,et al.  Synthesis of Some Arylsulfur Pentafluoride Pesticides and Their Relative Activities Compared to the Trifluoromethyl Analogues , 2004 .

[53]  J. Cannon,et al.  Borylation of aryldiazonium ions with N-heterocyclic carbene-palladium catalysts formed without added base. , 2003, Organic letters.

[54]  M. Vaultier,et al.  Monomeric (dialkylamino)boranes: a new and efficient boron source in palladium catalyzed C-B bond formation with aryl halides. , 2003, Chemical communications.

[55]  N. Miyaura,et al.  A stoichiometric aromatic CbondH borylation catalyzed by iridium(i)/2,2'-bipyridine complexes at room temperature. , 2002, Angewandte Chemie.

[56]  W. R. Dolbier,et al.  New and convenient method for incorporation of pentafluorosulfanyl (SF5) substituents into aliphatic organic compounds. , 2002, Organic letters.

[57]  A. Fürstner,et al.  Microwave-assisted synthesis of pinacol boronates from aryl chlorides catalyzed by a palladium/imidazolium salt system. , 2002, Organic letters.

[58]  N. Miyaura,et al.  Mild iridium-catalyzed borylation of arenes. High turnover numbers, room temperature reactions, and isolation of a potential intermediate. , 2002, Journal of the American Chemical Society.

[59]  B. Kariuki,et al.  A New Method for the Synthesis of Aromatic Sulfurpentafluorides and Studies of the Stability of the Sulfurpentafluoride Group in Common Synthetic Transformations , 2000 .

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

[61]  Watanabe,et al.  Palladium-catalyzed borylation of aryl halides or triflates with dialkoxyborane: A novel and facile synthetic route to arylboronates , 2000, The Journal of organic chemistry.

[62]  M. Heckmeier,et al.  Liquid Crystals Based on Hypervalent Sulfur Fluorides: Pentafluorosulfuranyl as Polar Terminal Group. , 1999, Angewandte Chemie.

[63]  Miki Murata,et al.  Novel Palladium(0)-Catalyzed Coupling Reaction of Dialkoxyborane with Aryl Halides: Convenient Synthetic Route to Arylboronates , 1997 .

[64]  Norio Miyaura,et al.  Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds , 1995 .

[65]  N. Miyaura,et al.  Palladium(0)-Catalyzed Cross-Coupling Reaction of Alkoxydiboron with Haloarenes: A Direct Procedure for Arylboronic Esters , 1995 .

[66]  G. Asensio,et al.  Acid-mediated reaction of bis(pyridine)iodonium(I) tetrafluoroborate with aromatic compounds. A selective and general iodination method , 1993 .

[67]  Miguel A. Rodríguez,et al.  ELECTROPHILIC ADDITIONS OF POSITIVE IODINE TO ALKYNES THROUGH AN IODONIUM MECHANISM , 1990 .

[68]  C. Galli Radical reactions of arenediazonium ions: An easy entry into the chemistry of the aryl radical , 1988 .

[69]  J. Schwartz,et al.  Organometallics , 1987, Science.

[70]  T. E. Cole,et al.  Organoboranes. 48. Improved procedures for the preparation of boronic and borinic esters , 1986 .

[71]  G. Asensio,et al.  I(py)2BF4, a New Reagent in Organic Synthesis: General Method for the 1,2‐Iodofunctionalization of Olefins , 1985 .

[72]  T. E. Cole,et al.  Organoboranes. 31. A simple preparation of boronic esters from organolithium reagents and selected trialkoxyboranes , 1983 .

[73]  M. Doyle,et al.  Alkyl nitrite-metal halide deamination reactions. 6. Direct synthesis of arenediazonium tetrafluoroborate salts from aromatic amines, tert-butyl nitrite, and boron trifluoride etherate in anhydrous media , 1979 .

[74]  H. Zollinger,et al.  Dediazoniation of Arenediazonium Ions in Homogeneous Solution. Part IX. Spectral Evidence for a Homolytic Mechanism Involving Pyridine Complexes , 1976 .

[75]  J. Chlebowski,et al.  Aprotic diazotization of aniline in the presence of iodine , 1968 .

[76]  R. Köster,et al.  Pyridines as Stabilisers of Free Boron Radicals , 1967 .

[77]  W. A. Sheppard ARYLSULFUR TRIFLUORIDES AND PENTAFLUORIDES , 1960 .

[78]  J. Young,et al.  Some Thermal Reactions of Perfluoroalkyl Derivatives of SF6 with Fluorocarbon Olefins1 , 1958 .

[79]  F. E. Rogers,et al.  Fluorocarbon Derivatives. I. Derivatives of Sulfur Hexafluoride , 1957 .

[80]  G. Röschenthaler,et al.  An improved method for the fluorination of arylsulfur chlorotetrafluorides to arylsulfur pentafluorides , 2014 .

[81]  N. Miyaura Cross-Coupling Reactions , 2002 .

[82]  R. Chambers,et al.  Microreactors for elemental fluorine , 1999 .

[83]  L. Wojnárovits,et al.  Rates of alkyl radical-iodine scavenging reactions in normal and cycloalkanes , 1996 .

[84]  T. Sakakura,et al.  Reaction of silyl enol ethers with arenediazonium salts. Part 1. α-Arylation of ketones , 1994 .

[85]  J. G. Saha,et al.  Arylations using diazonium tetrafluoroborate and pyridine , 1965 .

[86]  A. F. Clifford,et al.  483. Organometallic and organometalloidal fluorine compounds. Part VIII. The electrochemical fluorination of dimethyl sulphide and carbon disulphide , 1953 .

[87]  Synlett , 2022 .