2-Trifluoromethylated indoles via radical trifluoromethylation of isonitriles.

Either two or three C-C bonds are formed in the synthesis of 2-trifluoromethylindoles starting with readily prepared isonitriles and the Togni reagent as CF3 radical precursor. These transformations occur in the absence of transition metal, and products are obtained in moderate to good yields with excellent diastereoselectivity.

[1]  A. Studer,et al.  6-Phosphorylated phenanthridines from 2-isocyanobiphenyls via radical C-P and C-C bond formation. , 2014, Organic letters.

[2]  Shouyun Yu,et al.  Synthesis of 6-alkylated phenanthridine derivatives using photoredox neutral somophilic isocyanide insertion. , 2013, Angewandte Chemie.

[3]  C. Nevado,et al.  Metal-free aryltrifluoromethylation of activated alkenes. , 2013, Angewandte Chemie.

[4]  A. Studer,et al.  6-Aroylated phenanthridines via base promoted homolytic aromatic substitution (BHAS). , 2013, Organic letters.

[5]  T. Loh,et al.  Directing-group-assisted copper-catalyzed olefinic trifluoromethylation of electron-deficient alkenes. , 2013, Angewandte Chemie.

[6]  A. Studer,et al.  6-Trifluoromethyl-phenanthridines through radical trifluoromethylation of isonitriles. , 2013, Angewandte Chemie.

[7]  S. Buchwald,et al.  Enantioselective functionalization of radical intermediates in redox catalysis: copper-catalyzed asymmetric oxytrifluoromethylation of alkenes. , 2013, Angewandte Chemie.

[8]  S. Ma,et al.  Copper-catalyzed cyclic oxytrifluoromethylation of 2,3-allenoic acids to trifluoromethylated butenolides. , 2013, Chemistry.

[9]  C. Nevado,et al.  Copper-catalyzed one-pot trifluoromethylation/aryl migration/desulfonylation and C(sp2)-N bond formation of conjugated tosyl amides. , 2013, Journal of the American Chemical Society.

[10]  Bin Yang,et al.  Copper-catalyzed tandem trifluoromethylation/semipinacol rearrangement of allylic alcohols. , 2013, Angewandte Chemie.

[11]  A. Modak,et al.  Oxidative trifluoromethylation of unactivated olefins: an efficient and practical synthesis of α-trifluoromethyl-substituted ketones. , 2013, Angewandte Chemie.

[12]  Lei Zhou,et al.  PhI(OAc)2-mediated synthesis of 6-(trifluoromethyl)phenanthridines by oxidative cyclization of 2-isocyanobiphenyls with CF3SiMe3 under metal-free conditions. , 2013, Organic letters.

[13]  T. Ritter,et al.  Introduction of fluorine and fluorine-containing functional groups. , 2013, Angewandte Chemie.

[14]  Grégory Danoun,et al.  Sandmeyer trifluoromethylation of arenediazonium tetrafluoroborates. , 2013, Angewandte Chemie.

[15]  M. Sodeoka,et al.  Trifluoromethylation reactions for the synthesis of β-trifluoromethylamines. , 2013, Angewandte Chemie.

[16]  Valentina Pirovano,et al.  Gold(I) or silver catalyzed synthesis of α-indolylacrylates. , 2013, Organic letters.

[17]  O. Baudoin,et al.  Copper-catalyzed trifluoromethylation of N,N-dialkylhydrazones. , 2013, Angewandte Chemie.

[18]  M. Sodeoka,et al.  Alkene trifluoromethylation coupled with C-C bond formation: construction of trifluoromethylated carbocycles and heterocycles. , 2013, Angewandte Chemie.

[19]  B. Nachtsheim,et al.  Iodine in Modern Oxidation Catalysis , 2013, Synthesis.

[20]  C. Nevado,et al.  Regio- and enantioselective aminofluorination of alkenes. , 2013, Angewandte Chemie.

[21]  A. Studer,et al.  Cross dehydrogenative coupling via base-promoted homolytic aromatic substitution (BHAS): synthesis of fluorenones and xanthones. , 2013, Organic letters.

[22]  Q. Shen,et al.  Progress in Copper‐Mediated Formation of Trifluoromethylated Arenes , 2012 .

[23]  Yong-Qiang Wang,et al.  Palladium-catalyzed intermolecular C3 alkenylation of indoles using oxygen as the oxidant. , 2012, Organic letters.

[24]  N. Chatani,et al.  Modular synthesis of phenanthridine derivatives by oxidative cyclization of 2-isocyanobiphenyls with organoboron reagents. , 2012, Angewandte Chemie.

[25]  Armido Studer,et al.  A "Renaissance" in radical trifluoromethylation. , 2012, Angewandte Chemie.

[26]  A. Studer,et al.  Transition-metal-free trifluoromethylaminoxylation of alkenes. , 2012, Angewandte Chemie.

[27]  H. Neumann,et al.  Recent developments on the trifluoromethylation of (hetero)arenes. , 2012, Chemistry, an Asian journal.

[28]  K. Engle,et al.  Trifluoromethylation of allylsilanes under copper catalysis. , 2012, Chemistry.

[29]  Ye Wei,et al.  Palladium-catalyzed aerobic oxidative cyclization of N-aryl imines: indole synthesis from anilines and ketones. , 2012, Journal of the American Chemical Society.

[30]  M. Sodeoka,et al.  Copper-catalyzed trifluoromethylation of allylsilanes. , 2012, Angewandte Chemie.

[31]  Jinbo Hu,et al.  Copper-catalyzed di- and trifluoromethylation of α,β-unsaturated carboxylic acids: a protocol for vinylic fluoroalkylations. , 2012, Angewandte Chemie.

[32]  N. Iqbal,et al.  Trifluoromethylation of heterocycles via visible light photoredox catalysis , 2012 .

[33]  P. Pihko,et al.  Palladium-catalyzed dehydrogenative β'-functionalization of β-keto esters with indoles at room temperature. , 2012, Journal of the American Chemical Society.

[34]  A. Togni,et al.  Rhenium-Catalyzed Trifluoromethylation of Arenes and Heteroarenes by Hypervalent Iodine Reagents , 2012 .

[35]  B. Usachev,et al.  Regioselective synthesis of trifluoromethylated 3-(pyrazolyl)indoles on the basis of 6-(trifluoromethyl)comanic acid , 2012 .

[36]  Tao Wu,et al.  Palladium-catalyzed oxidative aryltrifluoromethylation of activated alkenes at room temperature. , 2012, Journal of the American Chemical Society.

[37]  George Coukos,et al.  Cancer immunotherapy comes of age , 2011, Nature.

[38]  D. MacMillan,et al.  Trifluoromethylation of arenes and heteroarenes by means of photoredox catalysis , 2011, Nature.

[39]  V. Matoušek,et al.  Synthesis of α-CF3-substituted carbonyl compounds with relative and absolute stereocontrol using electrophilic CF3-transfer reagents. , 2011, Organic letters.

[40]  J. Wang,et al.  Copper-catalyzed C(sp3)-C(sp3) bond formation using a hypervalent iodine reagent: an efficient allylic trifluoromethylation. , 2011, Journal of the American Chemical Society.

[41]  W. Su,et al.  Co/Mn-mediated oxidative cross-coupling of indoles with β-keto esters via dioxygen activation: an efficient access to ketonization-olefination of indoles. , 2011, Chemical communications.

[42]  T. Bach,et al.  Palladium-catalyzed direct 2-alkylation of indoles by norbornene-mediated regioselective cascade C-H activation. , 2011, Journal of the American Chemical Society.

[43]  S. Buchwald,et al.  Copper-catalyzed trifluoromethylation of unactivated olefins. , 2011, Angewandte Chemie.

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

[45]  Armido Studer,et al.  Organocatalysis and C-H activation meet radical- and electron-transfer reactions. , 2011, Angewandte Chemie.

[46]  G. Fabrizi,et al.  Update 1 of: Synthesis and functionalization of indoles through palladium-catalyzed reactions. , 2011, Chemical reviews.

[47]  A. Ogawa,et al.  Photoinduced intramolecular cyclization of o-ethenylaryl isocyanides with organic disulfides mediated by diphenyl ditelluride. , 2011, The Journal of organic chemistry.

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

[49]  G. Gribble,et al.  Trifluoromethylation of aryl and heteroaryl halides , 2011 .

[50]  Haibo Xie,et al.  Palladium-Catalyzed Synthesis of 2-Fluoroalkyl-3-methylene- 3H-indoles Through a Domino Carbopalladation/C-H Activation Process , 2011 .

[51]  M. Sodeoka,et al.  Direct C2-trifluoromethylation of indole derivatives catalyzed by copper acetate , 2010 .

[52]  G. Bartoli,et al.  Organocatalytic strategies for the asymmetric functionalization of indoles. , 2010, Chemical Society reviews.

[53]  Yunyang Wei,et al.  CeCl3-Catalyzed Reduction of Methyl Esters of Carboxylic Acids to Corresponding Alcohols with Sodium Borohydride , 2010 .

[54]  A. Togni,et al.  Electrophilic Trifluoromethylation of Arenes and N‐Heteroarenes Using Hypervalent Iodine Reagents. , 2010 .

[55]  N. Chatani,et al.  Synthesis of 2-boryl- and silylindoles by copper-catalyzed borylative and silylative cyclization of 2-alkenylaryl isocyanides. , 2010, The Journal of organic chemistry.

[56]  J. Hao,et al.  p-TsOH promoted Fischer indole synthesis of multi-substituted 2-trifluoromethyl indole derivatives , 2010 .

[57]  Valérie Pons,et al.  Catalytic oxyamidation of indoles. , 2010, Angewandte Chemie.

[58]  M. Bandini,et al.  Catalytic functionalization of indoles in a new dimension. , 2009, Angewandte Chemie.

[59]  V. Nenajdenko,et al.  α-Trifluoromethyl-β-aryl enamines in the synthesis of trifluoromethylated heterocycles by the Fischer and the Pictet-Spengler reactions , 2009 .

[60]  N. Jiao,et al.  Indoles from simple anilines and alkynes: palladium-catalyzed C-H activation using dioxygen as the oxidant. , 2009, Angewandte Chemie.

[61]  R. Fröhlich,et al.  Stereoselective palladium-catalyzed carboaminoxylations of indoles with arylboronic acids and TEMPO. , 2009, Angewandte Chemie.

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

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

[64]  A. Studer,et al.  Isonitrile trapping reactions under thermolysis of alkoxyamines for the synthesis of quinolines. , 2006, Organic letters.

[65]  P. Eisenberger,et al.  Novel 10-I-3 hypervalent iodine-based compounds for electrophilic trifluoromethylation. , 2006, Chemistry.

[66]  H. Tokuyama,et al.  Synthesis of 2,3-Dialkylindoles from 2-Alkenylphenylisocyanides and Imines by Silyltelluride- and Tin Hydride-Mediated Sequential Radical Reactions , 2005 .

[67]  H. Kagechika,et al.  A novel melatonin derivative modulates sleep–wake cycle in rats , 2004, Neuroscience Letters.

[68]  H. Tokuyama,et al.  Synthesis of 2,3-Disubstituted Indoles by Palladium-Mediated Coupling of 2-Iodoindoles , 2000 .

[69]  H. Furuta,et al.  Novel cyclopropapyrroloindole derivative (AT-3510) bearing methoxycarbonyl and trifluoromethyl groups. , 1999, Journal of medicinal chemistry.

[70]  Yoshihisa Kobayashi,et al.  Development of a Novel Indole Synthesis and Its Application to Natural Products Synthesis , 1998 .

[71]  H. Furuta,et al.  Synthesis and antitumor activity of novel cyclopropapyrroloindole(CPI) derivatives bearing methoxycarbonyl and trifluoromethyl groups , 1997 .

[72]  Wei‐yuan Huang,et al.  A new approach to polyfluoroalkyl imidoyl iodide , 1996 .

[73]  I. Ryu,et al.  Tandem Radical Reactions of Carbon Monoxide, Isonitriles, and Other Reagent Equivalents of the Geminal Radical Acceptor/Radical Precursor Synthon. , 1996, Chemical reviews.

[74]  T. Fukuyama,et al.  A Novel Tin-Mediated Indole Synthesis , 1994 .

[75]  J. Rokach,et al.  Synthesis, chemistry, and photochemical substitutions of 6,11-dihydro-5H-pyrrolo[2,1-b][3]benzazepin-11-ones , 1983 .

[76]  S. Buchwald,et al.  Copper-Catalyzed Oxytrifluoromethylation of Unactivated Alkenes , 2012 .

[77]  T. Yamakawa,et al.  Trifluoromethylation of various aromatic compounds by CF3I in the presence of Fe(II) compound, H2O2 and dimethylsulfoxide , 2010 .

[78]  T. Kawasaki,et al.  Simple indole alkaloids and those with a nonrearranged monoterpenoid unit. , 2005, Natural product reports.

[79]  H. Tokuyama,et al.  Indole synthesis by radical cyclization of o-alkenylphenyl isocyanides and its application to the total synthesis of natural products. , 2002, Chemical record.

[80]  Qing‐Yun Chen,et al.  Photoinduced electron-transfer reaction of difluorodiiodomethane with aza-aromatic compounds and enamines , 1993 .

[81]  Masato Yoshida,et al.  Perfluoroalkylations of nitrogen-containing heteroaromatic compounds with bis(perfluoroalkanoyl) peroxides , 1989 .

[82]  F. Bordwell,et al.  Acidities of carbon and nitrogen acids: the aromaticity of the cyclopentadienyl anion , 1981 .