Stereocontrolled Nucleophilic Fluorination at the Tertiary sp3-Carbon Center for Enantiopure Synthesis of 3-Fluorooxindoles.

The first asymmetric nucleophilic fluorination at the sp3-tertiary carbon center has been developed using inexpensive tetrabutylammonium fluoride (TBAF) without any metal/catalyst for the synthesis of 3-fluoro-3-substituted oxindoles with excellent enantioselectivity (ee up to >99%). Regio- and stereocontrolled ring opening of spiroaziridine with retention of configuration and other experiments revealed that the fluorination proceeded through an anchimeric assistance.

[1]  Sayan Roy,et al.  Domino Corey-Chaykovsky Reaction for One-Pot Access to Spirocyclopropyl Oxindoles. , 2018, Organic letters.

[2]  R. Paton,et al.  Asymmetric nucleophilic fluorination under hydrogen bonding phase-transfer catalysis , 2018, Science.

[3]  M. Sodeoka,et al.  Modern Approaches for Asymmetric Construction of Carbon-Fluorine Quaternary Stereogenic Centers: Synthetic Challenges and Pharmaceutical Needs. , 2018, Chemical reviews.

[4]  jin-quan yu,et al.  Controlling Pd(IV) reductive-elimination pathways enables Pd(II)-catalyzed enantioselective C(sp3)–H fluorination , 2018, Nature Chemistry.

[5]  S. Hajra,et al.  Catalyst-Free Ring Opening of Spiroaziridine Oxindoles by Heteronucleophiles: An Approach to the Synthesis of Enantiopure 3-Substituted Oxindoles. , 2018, The Journal of organic chemistry.

[6]  F. Fülöp,et al.  Recent advances in the transformations of cycloalkane-fused oxiranes and aziridines , 2017 .

[7]  S. Hajra,et al.  Catalyst-Free "On-Water" Regio- and Stereospecific Ring-Opening of Spiroaziridine Oxindole: Enantiopure Synthesis of Unsymmetrical 3,3'-Bisindoles. , 2017, Organic letters.

[8]  Kodai Nishi,et al.  Ionic Liquid-Mediated Hydrofluorination of o-Azaxylylenes Derived from 3-Bromooxindoles. , 2017, Organic letters.

[9]  K. Balaraman,et al.  Catalytic Enantioselective and Diastereoselective Allylic Alkylation with Fluoroenolates: Efficient Access to C3-Fluorinated and All-Carbon Quaternary Oxindoles. , 2017, Angewandte Chemie.

[10]  J. Hartwig,et al.  Palladium-Catalyzed, Enantioselective α-Arylation of α-Fluorooxindoles. , 2016, Organic letters.

[11]  Ryo Fujimoto,et al.  Site-Selective Tertiary Alkyl-Fluorine Bond Formation from α-Bromoamides Using a Copper/CsF Catalyst System. , 2016, Angewandte Chemie.

[12]  Yi Pan,et al.  Detrifluoroacetylative in Situ Generation of Free 3-Fluoroindolin-2-one-Derived Tertiary Enolates: Design, Synthesis, and Assessment of Reactivity toward Asymmetric Mannich Reactions. , 2016, Organic letters.

[13]  S. Hajra,et al.  Synthesis of Chiral Spiro-Aziridine Oxindoles via Aza-Corey-Chaykovsky Reaction of Isatin Derived N-tert-Butanesulfinyl Ketimines. , 2016, Organic letters.

[14]  Wei Zhu,et al.  Next Generation of Fluorine-Containing Pharmaceuticals, Compounds Currently in Phase II-III Clinical Trials of Major Pharmaceutical Companies: New Structural Trends and Therapeutic Areas. , 2016, Chemical reviews.

[15]  M. D. Hill,et al.  Applications of Fluorine in Medicinal Chemistry. , 2015, Journal of medicinal chemistry.

[16]  M. Haukka,et al.  A novel and selective fluoride opening of aziridines by XtalFluor-E. synthesis of fluorinated diamino acid derivatives. , 2015, Organic letters.

[17]  Robert J. Phipps,et al.  Advances in Catalytic Enantioselective Fluorination, Mono-, Di-, and Trifluoromethylation, and Trifluoromethylthiolation Reactions , 2014, Chemical reviews.

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

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

[20]  J. Kalow,et al.  Enantioselective fluoride ring opening of aziridines enabled by cooperative Lewis acid catalysis , 2013 .

[21]  T. Ritter,et al.  Late-stage deoxyfluorination of alcohols with PhenoFluor. , 2013, Journal of the American Chemical Society.

[22]  Jie-Xing Zhou,et al.  Synthesis of β-Fluoro Amides Using Partially Hydrated Nickel Difluoride as Fluorine Source , 2012, Synlett.

[23]  J. Kalow,et al.  Synthesis of β-fluoroamines by Lewis base catalyzed hydrofluorination of aziridines. , 2012, The Journal of organic chemistry.

[24]  L. Cavallo,et al.  Synthesis of 3-fluoro-3-aryl oxindoles: direct enantioselective α arylation of amides. , 2012, Angewandte Chemie.

[25]  J. Kalow,et al.  Mechanistic investigations of cooperative catalysis in the enantioselective fluorination of epoxides. , 2011, Journal of the American Chemical Society.

[26]  S. Hajra,et al.  Catalytic enantioselective aziridoarylation of aryl cinnamyl ethers toward synthesis of trans-3-amino-4-arylchromans. , 2011, The Journal of organic chemistry.

[27]  Alan A. Wilson,et al.  Regioselective ring opening of 2-methylaziridine derivatives with 18F- and 19F-fluoride , 2011 .

[28]  S. Hajra,et al.  Catalytic enantioselective synthesis of A-86929, a dopamine D1 agonist. , 2011, Chemical communications.

[29]  V. V. Speybroeck,et al.  Systematic Study of Halide-Induced Ring Opening of 2-Substituted Aziridinium Salts and Theoretical Rationalization of the Reaction Pathways , 2010 .

[30]  J. Kalow,et al.  Enantioselective ring opening of epoxides by fluoride anion promoted by a cooperative dual-catalyst system. , 2010, Journal of the American Chemical Society.

[31]  B. Maji,et al.  A Catalytic and Enantioselective Synthesis of trans-2-Amino-1- aryltetralins , 2009 .

[32]  Alan A. Wilson,et al.  [18F]Fluoroamines via ring-opening of N-Cbz-2-methylaziridine with [18F]-fluoride , 2009 .

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

[34]  N. Shibata,et al.  Cinchona alkaloid catalyzed enantioselective fluorination of allyl silanes, silyl enol ethers, and oxindoles. , 2008, Angewandte Chemie.

[35]  M. D’hooghe,et al.  Opposite regioselectivity in the sequential ring-opening of 2-(alkanoyloxymethyl)aziridinium salts by bromide and fluoride in the synthesis of functionalized β-fluoro amines , 2006 .

[36]  N. Shibata,et al.  Highly enantioselective catalytic fluorination and chlorination reactions of carbonyl compounds capable of two-point binding. , 2005, Angewandte Chemie.

[37]  M. Sodeoka,et al.  Catalytic enantioselective fluorination of oxindoles. , 2005, Journal of the American Chemical Society.

[38]  Yong‐Gui Zhou,et al.  Facile preparation of beta-fluoro amines by the reaction of aziridines with potassium fluoride dihydrate in the presence of Bu4NHSO4. , 2004, The Journal of organic chemistry.

[39]  T. Asahi,et al.  Enantioselective fluorination mediated by cinchona alkaloid derivatives/Selectfluor combinations: reaction scope and structural information for N-fluorocinchona alkaloids. , 2001, Journal of the American Chemical Society.