Efficient copper-catalyzed trifluoromethylation of aromatic and heteroaromatic iodides: the beneficial anchoring effect of borates.

Efficient copper-catalyzed trifluoromethylation of aromatic iodides was achieved with TMSCF3 in the presence of trimethylborate. The Lewis acid was used to anchor the in situ generated trifluoromethyl anion and suppress its rapid decomposition. Broad applicability of the new trifluoromethylating reaction was demonstrated in the functionalization of different aromatic and heteroaromatic iodides.

[1]  Qun Liu,et al.  Trifluoromethyltrimethylsilane: nucleophilic trifluoromethylation and beyond. , 2015, Chemical reviews.

[2]  C. Nevado,et al.  Addition of CF3 across unsaturated moieties: a powerful functionalization tool , 2014, Chemical Society reviews.

[3]  F. Qing,et al.  Oxidative trifluoromethylation and trifluoromethylthiolation reactions using (trifluoromethyl)trimethylsilane as a nucleophilic CF3 source. , 2014, Accounts of chemical research.

[4]  K. Mikami,et al.  Direct synthesis of a trifluoromethyl copper reagent from trifluoromethyl ketones: application to trifluoromethylation. , 2013, Chemistry.

[5]  Y. Itoh,et al.  Cu-catalyzed trifluoromethylation of aryl iodides with trifluoromethylzinc reagent prepared in situ from trifluoromethyl iodide , 2013, Beilstein journal of organic chemistry.

[6]  S. Barata‐Vallejo,et al.  Metal-mediated radical perfluoroalkylation of organic compounds , 2013 .

[7]  Pinhong Chen,et al.  Recent Advances in Transition-Metal-Catalyzed Trifluoromethylation and Related Transformations , 2013, Synthesis.

[8]  S. Buchwald,et al.  Rapid and efficient trifluoromethylation of aromatic and heteroaromatic compounds using potassium trifluoroacetate enabled by a flow system. , 2013, Angewandte Chemie.

[9]  M. A. Novikov,et al.  Trifluoromethylation of aryl and heteroaryl halides with fluoroform-derived CuCF3: scope, limitations, and mechanistic features. , 2013, The Journal of organic chemistry.

[10]  Jinhua J. Song,et al.  Development of a Safe and Economical Synthesis of Methyl 6-Chloro-5-(trifluoromethyl)nicotinate: Trifluoromethylation on Kilogram Scale , 2013 .

[11]  G. Olah,et al.  Taming of Fluoroform: Direct Nucleophilic Trifluoromethylation of Si, B, S, and C Centers , 2012, Science.

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

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

[14]  M. Sanford,et al.  Investigations into Transition Metal Catalyzed Arene Trifluoromethylation Reactions. , 2012, Synlett : accounts and rapid communications in synthetic organic chemistry.

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

[16]  M. Beller,et al.  Towards a Practical and Efficient Copper-Catalyzed Trifluoromethylation of Aryl Halides , 2012, Topics in Catalysis.

[17]  F. Qing,et al.  Copper-catalyzed oxidative trifluoromethylation of terminal alkynes and aryl boronic acids using (trifluoromethyl)trimethylsilane. , 2012, The Journal of organic chemistry.

[18]  F. Qing,et al.  Copper-catalyzed direct C-H oxidative trifluoromethylation of heteroarenes. , 2012, Journal of the American Chemical Society.

[19]  Q. Shen,et al.  Highly selective trifluoromethylation of 1,3-disubstituted arenes through iridium-catalyzed arene borylation. , 2012, Angewandte Chemie.

[20]  M. A. Novikov,et al.  Direct cupration of fluoroform. , 2011, Journal of the American Chemical Society.

[21]  M. Sanford,et al.  Silver-mediated trifluoromethylation of arenes using TMSCF3. , 2011, Organic letters.

[22]  D. Blackmond,et al.  Innate C-H trifluoromethylation of heterocycles , 2011, Proceedings of the National Academy of Sciences.

[23]  V. Grushin,et al.  Simple, stable, and easily accessible well-defined CuCF3 aromatic trifluoromethylating agents. , 2011, Angewandte Chemie.

[24]  Kun Jin,et al.  A Ligand-Free Copper-Catalyzed Decarboxylative Trifluoromethylation of Aryliodides with Sodium Trifluoroacetate Using Ag2O as a Promoter , 2011 .

[25]  G. Kabalka,et al.  A novel catalytic process for trifluoromethylation of bromoaromatic compounds. , 2011, Chemical communications.

[26]  S. Lindeman,et al.  Copper-catalyzed arylation of 1H-perfluoroalkanes. , 2011, Journal of the American Chemical Society.

[27]  Guosheng Liu,et al.  Palladium-catalyzed oxidative trifluoromethylation of indoles at room temperature. , 2011, Chemistry.

[28]  Kuo‐Wei Huang,et al.  Cooperative Effect of Silver in Copper-Catalyzed Trifluoromethylation of Aryl Iodides Using Me3SiCF3 , 2011 .

[29]  H. Amii,et al.  Copper‐Catalyzed Aromatic Trifluoromethylation via Group Transfer from Fluoral Derivatives , 2011 .

[30]  J. Hartwig,et al.  A broadly applicable copper reagent for trifluoromethylations and perfluoroalkylations of aryl iodides and bromides. , 2011, Angewandte Chemie.

[31]  Q. Shen,et al.  Copper-catalyzed trifluoromethylation of aryl and vinyl boronic acids with an electrophilic trifluoromethylating reagent. , 2011, Organic letters.

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

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

[34]  Lei Liu,et al.  Copper-catalyzed trifluoromethylation of aryl boronic acids using a CF3+ reagent. , 2011, Chemical communications.

[35]  G. Röschenthaler,et al.  Copper-catalyzed trifluoromethylation of aryl iodides with potassium (trifluoromethyl)trimethoxyborate. , 2011, Chemistry.

[36]  Ji‐Chang Xiao,et al.  Copper-mediated trifluoromethylation of heteroaromatic compounds by trifluoromethyl sulfonium salts. , 2011, Angewandte Chemie.

[37]  S. Buchwald,et al.  Room temperature aryl trifluoromethylation via copper-mediated oxidative cross-coupling. , 2011, The Journal of organic chemistry.

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

[39]  Jun‐An Ma,et al.  Combination Catalysis in Enantioselective Trifluoromethylation , 2010 .

[40]  S. Buchwald,et al.  The Palladium-Catalyzed Trifluoromethylation of Aryl Chlorides , 2010, Science.

[41]  jin-quan yu,et al.  Pd(II)-catalyzed ortho-trifluoromethylation of arenes using TFA as a promoter. , 2010, Journal of the American Chemical Society.

[42]  H. Amii,et al.  Aromatic trifluoromethylation catalytic in copper. , 2009, Chemical communications.

[43]  D. Vicic,et al.  Structure of Bis(trifluoromethyl)cuprate and Its Role in Trifluoromethylation Reactions , 2008 .

[44]  W. Hagmann,et al.  The many roles for fluorine in medicinal chemistry. , 2008, Journal of medicinal chemistry.

[45]  David A. Vicic,et al.  Active trifluoromethylating agents from well-defined Copper(I)-CF3 complexes. , 2008, Journal of the American Chemical Society.

[46]  K. Kirk.  Fluorination in Medicinal Chemistry: Methods, Strategies, and Recent Developments , 2008 .

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

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

[49]  M. Schlosser.  CF(3)-bearing aromatic and heterocyclic building blocks. , 2006, Angewandte Chemie.

[50]  M. A. McClinton,et al.  Trifluoromethylations and related reactions in organic chemistry , 1992 .

[51]  Masato Yoshida,et al.  Trifluoromethylation of aromatic compounds with bis(trifluoroacetyl) peroxide , 1990 .

[52]  A. I. Mushta,et al.  Me3SiCF3/AgF/Cu—A new reagents combination for selective trifluoromethylation of various organic halides by trifluoromethylcopper, CuCF3 , 2012 .

[53]  T. Fuchikami,et al.  A novel and convenient method for trifluoromethylation of organic halides using CF3SiR'3/KF/Cu(I) system , 1991 .

[54]  Yoshiro Kobayashi,et al.  Trifluoromethylation of aromatic compounds , 1969 .