Pd-Catalyzed Asymmetric Hydrogenation of α-Fluorinated Iminoesters in Fluorinated Alcohol: A New and Catalytic Enantioselective Synthesis of Fluoro α-Amino Acid Derivatives

Under hydrogen pressure, a catalytic amount of palladium(II) trifluoroacetate and 2,2‘-bis(diphenylphosphino)-1,1‘-binaphthyl (BINAP) promoted asymmetric hydrogenation of α-fluorinated iminoesters to afford highly enantioenriched β-fluorinated α-amino esters. The yield and ee were much improved by employing fluorinated alcohols such as 2,2,2-trifluoroethanol (up to 91% ee).

[1]  H. Amii,et al.  Palladium-catalyzed tert-butoxycarbonylation of trifluoroacetimidoyl iodides. , 2000, The Journal of organic chemistry.

[2]  H. Jacobsen,et al.  PROBING REGIOSELECTIVE INTERMOLECULAR HYDROGEN BONDING TO RE(CO)H2(NO)(PR3)2 COMPLEXES BY NMR TITRATION AND EQUILIBRIUM NMR METHODOLOGIES , 1999 .

[3]  K. Uneyama.  Chemistries of trifluoroacetimidoyl halides: preparation, reactions, and applications for the synthesis of fluorinated heterocycles , 1999 .

[4]  H. Ishitani,et al.  Catalytic enantioselective addition to imines. , 1999, Chemical reviews.

[5]  A. Volonterio,et al.  Two Practical and Efficient Approaches to Fluorinated and Nonfluorinated Chiral beta-Imino Sulfoxides. , 1998, The Journal of organic chemistry.

[6]  A. L. Chistyakov,et al.  UNUSUAL HYDROGEN BONDS WITH A HYDRIDE ATOM IN BORON HYDRIDES ACTING AS PROTON ACCEPTOR. SPECTROSCOPIC AND THEORETICAL STUDIES , 1998 .

[7]  J. Ayllón,et al.  Influence of hydrogen bonding on the spectroscopic properties and on the reactivity of ruthenium hydride dihydrogen complexes , 1998 .

[8]  E. Zangrando,et al.  Bis-Chelated Palladium(II) Complexes with Nitrogen-Donor Chelating Ligands Are Efficient Catalyst Precursors for the CO/Styrene Copolymerization Reaction , 1997 .

[9]  K. Ishikawa,et al.  Transition Metal/Base-Catalyzed Aldol Reactions of Isocyanoacetic Acid Derivatives with Prochiral Ketones, a Straightforward Approach to Stereochemically Defined β,β-Disubstituted-β-hydroxy-α-amino Acids.1 Scope and Limitations , 1997 .

[10]  S. V. Meille,et al.  Synthesis of optically pure (R)- and (S)-α-trifluoromethyl-alanine , 1994 .

[11]  V. Soloshonok,et al.  Catalytic asymmetric synthesis of β-fluoroalkyl-β-amino acids via biomimetic [1,3]-proton shift reaction , 1994 .

[12]  K. Yanagi,et al.  Palladium-catalyzed asymmetric arylation of 2,3-dihydrofuran with phenyl triflate. A novel asymmetric catalysis involving a kinetic resolution process , 1993 .

[13]  C. Bolm.  Enantioselective transition metal-catalyzed hydrogenation for the asymmetric synthesis of amines , 1993 .

[14]  S. Buchwald,et al.  Asymmetric titanocene-catalyzed hydrogenation of imines , 1992 .

[15]  K. Uneyama,et al.  Homologation of trifluoroacetimidoyl iodides by palladium-catalyzed carbonylation. An approach to α-amino perfluoroalkanoic acids. , 1992 .

[16]  W. Cullen,et al.  Catalytic asymmetric hydrogenation of imines. Use of rhodium(I)/phosphine complexes and characterization of rhodium(I)/imine complexes , 1991 .

[17]  B. Pugin,et al.  Novel Diphosphinoiridium Catalysts for the Enantioselective Hydrogenation of N-Arylketimines , 1990 .

[18]  A. Cutler,et al.  Studies on carbonylating organoiron alkyl complexes (.eta.-C5H5)(CO)(L)FeR , 1985 .

[19]  H. Teunissen.  Homogeneous ruthenium catalyzed hydrogenation of esters to alcohols , 1998 .

[20]  K. Uneyama,et al.  Asymmetric reduction of 2-(N-arylimino)-3,3,3-trifluoropropanoic acid esters leading to enantiomerically enriched 3,3,3-trifluoroalanine , 1996 .

[21]  V. Soloshonok,et al.  Gold(I)-catalyzed asymmetric aldol reactions of isocyanoacetic acid derivatives with fluoroaryl aldehydes , 1996 .

[22]  G. Bernardinelli,et al.  Chiral toluene-2,α-sultam auxiliaries: Preparation and structure of enantiomerically pure (2R)- and (S)-ethyl-2,1′-sultam ☆ , 1990 .

[23]  Norbert Sewald,et al.  α-Trifluormethyl-substituierte Aminosäuren mit Acetylenfunktionen in der Seitenkette , 1990 .

[24]  J. Welch.  Tetrahedron report number 221 , 1987 .