Highly regio- and stereoselective trans-iodofluorination of ynamides enabling the synthesis of (E)-α-fluoro-β-iodoenamides.

A highly regio- and stereoselective trans-iodofluorination reaction of ynamides with NIS and Et3N·3HF has been achieved, affording (E)-α-fluoro-β-iodoenamides in moderate to good yields. The reaction proceeds under mild reaction conditions and exhibits good functional group compatibility.

[1]  Yu Tang,et al.  Regioselective TfOH-mediated hydroamidation of ynamides with nitriles , 2017 .

[2]  Lin Zhu,et al.  Silver-catalyzed radical carbofluorination of unactivated alkenes with acetic acid in aqueous solution , 2017 .

[3]  Jian Zhou,et al.  Highly Stereoselective Gold-Catalyzed Coupling of Diazo Reagents and Fluorinated Enol Silyl Ethers to Tetrasubstituted Alkenes. , 2017, Angewandte Chemie.

[4]  Hao Xu,et al.  Iron(II)-Catalyzed Intermolecular Aminofluorination of Unfunctionalized Olefins Using Fluoride Ion. , 2016, Journal of the American Chemical Society.

[5]  Hongjun Zhu,et al.  (IPr)CuF-catalyzed α-site regiocontrolled trans-hydrofluorination of ynamides. , 2016, Organic & biomolecular chemistry.

[6]  A. Sahoo,et al.  Dimethyl Sulfoxide and N-Iodosuccinimide Promoted 5-exo-dig Oxidative Cyclization of Yne-Tethered Ynamide: Access to Pyrrolidones and Spiro-pyrrolidones. , 2016, Organic letters.

[7]  Stefan A. Ruider,et al.  Divergent ynamide reactivity in the presence of azides – an experimental and computational study , 2016, Chemical science.

[8]  K. Szabó,et al.  Rhodium‐Catalyzed Geminal Oxyfluorination and Oxytrifluoro‐Methylation of Diazocarbonyl Compounds , 2016, Angewandte Chemie.

[9]  Hongjun Zhu,et al.  Cu(I)- or Ag(I)-Catalyzed Regio- and Stereocontrolled trans-Hydrofluorination of Ynamides. , 2016, Organic letters.

[10]  S. Hara,et al.  Stereoselective synthesis of iodofluoroalkenes by iodofluorination of alkynes using IF5-pyridine-HF , 2016 .

[11]  N. Endo,et al.  Elucidation of reaction process through β-halogen elimination in CuCN-mediated cyanation of ( E )-1-bromo-2-iodoalkene , 2016 .

[12]  K. Szabó,et al.  Palladium-Catalyzed Iodofluorination of Alkenes Using Fluoro-Iodoxole Reagent , 2016 .

[13]  Hua Yang,et al.  Transition-Metal-Free Oxyfluorination of Olefinic Amides for the Synthesis of Fluorinated Heterocycles. , 2015, The Journal of organic chemistry.

[14]  Ying He,et al.  Palladium-Catalyzed Enantioselective 1,1-Fluoroarylation of Aminoalkenes , 2015, Journal of the American Chemical Society.

[15]  Jinbo Hu,et al.  Diphenyliodonium-Catalyzed Fluorination of Arynes: Synthesis of ortho-Fluoroiodoarenes. , 2015, Angewandte Chemie.

[16]  Haodong Yang,et al.  Silver-catalyzed Meerwein arylation: intermolecular and intramolecular fluoroarylation of styrenes. , 2015, Chemical communications.

[17]  Xiaolin Zhu,et al.  Controlled Synthesis of 1,3,5-Oxadiazin-2-ones and Oxazolones through Regioselective Iodocyclization of Ynamides. , 2015, Organic letters.

[18]  P. Champagne,et al.  Monofluorination of Organic Compounds: 10 Years of Innovation. , 2015, Chemical reviews.

[19]  J. Marrot,et al.  Chemo- and stereoselective synthesis of fluorinated enamides from ynamides in HF/pyridine: second-generation approach to potent ureas bioisosteres. , 2015, The Journal of organic chemistry.

[20]  Lin Zhu,et al.  Formal fluorine atom transfer radical addition: silver-catalyzed carbofluorination of unactivated alkenes with ketones in aqueous solution , 2014 .

[21]  A. Slawin,et al.  Hydrofluorination of Alkynes Catalysed by Gold Bifluorides , 2014, ChemCatChem.

[22]  M. Heinrich,et al.  Intermolecular radical carbofluorination of non-activated alkenes. , 2014, Chemistry.

[23]  J. Che,et al.  Silver-promoted trans-hydrofluorination of ynamides: a regio- and stereoselective approach to (Z)-α-fluoroenamides , 2014 .

[24]  Xiaolin Zhu,et al.  Iodine‐Mediated Oxidation of Ynamides: A Facile Access to N‐Monosubstituted α‐Ketoamides and α‐Ketoimides , 2014 .

[25]  Ren‐Jie Song,et al.  Synthesis of 5‐(Fluoromethyl)‐4,5‐dihydroisoxazoles by Silver‐ Catalyzed Oxyfluorination of Unactivated Alkenes , 2014 .

[26]  G. Hammond,et al.  Designer HF-Based Fluorination Reagent: Highly Regioselective Synthesis of Fluoroalkenes and gem-Difluoromethylene Compounds from Alkynes , 2014, Journal of the American Chemical Society.

[27]  Lan-Gui Xie,et al.  A Brønsted acid catalyzed redox arylation. , 2014, Angewandte Chemie.

[28]  Qiang Yang,et al.  Metal-free, efficient oxyfluorination of olefins for the synthesis of α-fluoroketones. , 2014, Organic letters.

[29]  Hong Liu,et al.  Fluorine in pharmaceutical industry: fluorine-containing drugs introduced to the market in the last decade (2001-2011). , 2014, Chemical reviews.

[30]  C. Fu,et al.  C-F bond formation with fluoride anions--highly selective iodofluorination of simple allenes. , 2013, Chemical communications.

[31]  Huanfeng Jiang,et al.  Silver‐Assisted Difunctionalization of Terminal Alkynes: Highly Regio‐ and Stereoselective Synthesis of Bromofluoroalkenes , 2012 .

[32]  Guosheng Liu Transition metal-catalyzed fluorination of multi carbon-carbon bonds: new strategies for fluorinated heterocycles. , 2012, Organic & biomolecular chemistry.

[33]  J. Marrot,et al.  Stereoselective hydrofluorination of ynamides: a straightforward synthesis of novel α-fluoroenamides. , 2012, Chemical communications.

[34]  G. Evano,et al.  Click-alkynylation of N- and P-nucleophiles by oxidative cross-coupling with alkynylcopper reagents: a general synthesis of ynamides and alkynylphosphonates , 2012 .

[35]  F. Couty,et al.  Copper-catalyzed alkynylation of amides with potassium alkynyltrifluoroborates: a room-temperature, base-free synthesis of ynamides. , 2010, Organic letters.

[36]  Tao Wu,et al.  Palladium-catalyzed intramolecular aminofluorination of unactivated alkenes. , 2009, Journal of the American Chemical Society.

[37]  Scott J. Miller,et al.  Regio- and stereoselective synthesis of fluoroalkenes by directed Au(I) catalysis. , 2009, Organic letters.

[38]  F. Couty,et al.  Copper-mediated coupling of 1,1-dibromo-1-alkenes with nitrogen nucleophiles: a general method for the synthesis of ynamides. , 2009, Angewandte Chemie.

[39]  A. Gee,et al.  Synthesis of 11C, 18F, 15O, and 13N radiolabels for positron emission tomography. , 2008, Angewandte Chemie.

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

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

[42]  P. Müller,et al.  Reversible C-F bond formation and the Au-catalyzed hydrofluorination of alkynes. , 2007, Journal of the American Chemical Society.

[43]  Yanshi Zhang Synthesis of vinylpyrroles, vinylfurans and vinylindoles via a Brønsted acid catalyzed highly regio- and stereoselective cis-hydroarylation of ynamides , 2006 .

[44]  P. Conte,et al.  Iodofluorination of alkenes and alkynes promoted by iodine and 4-iodotoluene difluoride , 2006 .

[45]  Yanshi Zhang Syntheses of vinylindoles via a Brønsted acid catalyzed highly regio- and stereoselective cis-hydroarylation of ynamides ☆ , 2005 .

[46]  P. Jeschke The Unique Role of Fluorine in the Design of Active Ingredients for Modern Crop Protection , 2004, Chembiochem : a European journal of chemical biology.

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

[48]  G. Haufe,et al.  Synthesis of monofluorinated C4-building blocks based on methallyl chloride , 1995 .

[49]  A. Hedhli,et al.  Bromofluorination of Vinyloxiranes , 1994 .

[50]  G. Asensio,et al.  Regio- and stereoselective iodofluorination of alkenes with bis(pyridine)iodonium(I) tetrafluoroborate , 1991 .

[51]  T. Hiyama,et al.  Halofluorination of alkenes using tetrabutylammonium dihydrogentrifluoride , 1991 .

[52]  Á. Guerrero,et al.  Efficient utilization of tetrabutylammonium bifluoride in halofluorination reactions , 1989 .

[53]  G. Haufe,et al.  Triethylamine Tris-hydrofluoride [(C2H5)3N·3HF]: A Highly Versatile Source of Fluoride Ion for the Halofluorination of Alkenes , 1987 .

[54]  R. D. Evans,et al.  Iodofluorination of Alkenes Using Bis(sym-collidine)iodine(I) Tetrafluoroborate , 1987 .

[55]  M. Zupan,et al.  Polymers as reagents and catalysts. XI: Stereospecific iodofluorination of alkenes in the presence of polymer supported hydrogen fluoride , 1987 .

[56]  G. P. Ellis,et al.  Cyanation of aromatic halides , 1987 .

[57]  J. Olah,et al.  Synthetic methods and reactions. 63. Pyridinium poly(hydrogen fluoride) (30% pyridine-70% hydrogen fluoride): a convenient reagent for organic fluorination reactions , 1979 .

[58]  M. Zupan,et al.  Iodofluorination of phenyl-substituted olefins with methyliodine(III) difluoride , 1976 .

[59]  Jian Zhou,et al.  Recent Advances in the Highly Stereoselective Synthesis of Tri-or Tetra-substituted Monofluoroalkenes , 2017 .

[60]  A. Sahoo,et al.  Triphenylphosphine promoted regio and stereoselective α-halogenation of ynamides , 2016 .

[61]  X. Bi,et al.  Metal-free hydroacyloxylation and hydration reactions of ynamides: synthesis of α-acyloxyenamides and N-acylsulfonamides , 2015 .

[62]  R. Hagiwara,et al.  Fluorination with ionic liquid EMIMF(HF)2.3 as mild HF source , 2006 .

[63]  Tsuyoshi Fukuhara,et al.  Stereo- and regio-selective addition of iodotoluene difluoride to alk-1-ynes. Selective synthesis of 2-fluoro-1-iodoalk-1-enes , 1998 .