A novel one-pot reaction involving organocopper-mediated reduction/transmetalation/asymmetric alkylation, leading to the diastereoselective synthesis of functionalized (Z)-fluoroalkene dipeptide isosteres.

By a novel one-pot reaction sequence involving consecutive organocopper-mediated reduction, transmetalation and asymmetric alkylation, a highly diastereoselective synthesis of functionalized (Z)-fluoroalkene dipeptide isosteres was achieved in good to excellent yields.

[1]  A. Otaka,et al.  Unequivocal synthesis of (Z)-alkene and (E)-fluoroalkene dipeptide isosteres to probe structural requirements of the peptide transporter PEPT1. , 2006, Organic letters.

[2]  A. Saito,et al.  Stereoselective synthesis of (Z)-fluoroalkenes directed to peptide isosteres: copper mediated reaction of trialkylaluminum with 4,4-difluoro-5-hydroxyallylic alcohol derivatives , 2005 .

[3]  Scott J. Miller,et al.  Peptide bond isosteres: ester or (E)-alkene in the backbone of the collagen triple helix. , 2005, Organic letters.

[4]  P. Wipf,et al.  Electrostatic versus steric effects in peptidomimicry: synthesis and secondary structure analysis of gramicidin S analogues with (E)-alkene peptide isosteres. , 2005, Journal of the American Chemical Society.

[5]  A. Lambeir,et al.  Fluoro-olefins as peptidomimetic inhibitors of dipeptidyl peptidases. , 2005, Journal of medicinal chemistry.

[6]  J. Trent,et al.  Stereoselective synthesis of [L-Arg-L/D-3-(2-naphthyl)alanine]-type (E)-alkene dipeptide isosteres and its application to the synthesis and biological evaluation of pseudopeptide analogues of the CXCR4 antagonist FC131. , 2005, Journal of medicinal chemistry.

[7]  P. Wipf,et al.  Convergent approach to (E)-alkene and cyclopropane peptide isosteres. , 2005, Organic letters.

[8]  T. Kinoshita,et al.  SmI2-Mediated Reduction of γ,γ-Difluoro-α,β-enoates with Application to the Synthesis of Functionalized (Z)-Fluoroalkene-Type Dipeptide Isosteres , 2004 .

[9]  A. Otaka,et al.  Application of samarium diiodide (SmI2)-induced reduction of γ-acetoxy-α,β-enoates with α-specific kinetic electrophilic trapping for the synthesis of amino acid derivatives , 2003 .

[10]  A. Otaka,et al.  Diastereoselective synthesis of new psi[(E)-CH=CMe]- and psi[(Z)-CH=CMe]-type alkene dipeptide isosteres by organocopper reagents and application to conformationally restricted cyclic RGD peptidomimetics. , 2002, The Journal of organic chemistry.

[11]  P. Steel Recent developments in lanthanide mediated organic synthesis , 2001 .

[12]  A. Otaka,et al.  New access to α-substituted (Z)-fluoroalkene dipeptide isosteres utilizing organocopper reagents under ‘reduction–oxidative alkylation (R–OA)’ conditions , 2001 .

[13]  A. Otaka,et al.  Synthesis of (Z)-fluoroalkene dipeptide isosteres utilizing organocopper-mediated reduction of γ,γ-difluoro-α,β-enoates , 2001 .

[14]  A. Krief,et al.  Coupling of Organic Halides with Carbonyl Compounds Promoted by SmI(2), the Kagan Reagent. , 1999, Chemical reviews.

[15]  G. Molander,et al.  Sequenced reactions with samarium(II) iodide , 1998 .

[16]  P. Savignac,et al.  A new route to α-fluorovinylphosphonates utilizing Peterson olefination methodology , 1996 .

[17]  G. Molander Application of lanthanide reagents in organic synthesis , 1992 .

[18]  Masaaki Suzuki,et al.  Prostaglandin synthesis. 16. The three-component coupling synthesis of prostaglandins , 1988 .

[19]  Yoshinori Yamamoto,et al.  Reduction-alkylation with organocopper(I) reagents-alkyl halides: highly regioselective α-alkylation of γ-acetoxy-α,β-enoates with lithium dibutylcuprate-alkyl halides and difference in the reactivity of electron-deficient olefins with organocopper(I)-Lewis acid reagents , 1986 .

[20]  Yoshinori Yamamoto,et al.  DIFFERENCES IN THE REACTION OF ELECTRON DEFICIENT OLEFINS WITH ORGANOCOPPER(I)-LEWIS ACID REAGENTS AND EVIDENCE FOR A DIANIONIC EQUIVALENT , 1985 .

[21]  Masaaki Suzuki,et al.  Prostaglandin synthesis. 10. An extremely short way to prostaglandins , 1985 .

[22]  K. Itoh,et al.  Conjugate addition of lithiotrimethylsilylacetate. A simple synthesis of methyl jasmonate via vicinal double alkylation , 1984 .

[23]  K. Itoh,et al.  New stereocontrolled approach to some insect pheromones via silicon-directed beckmann fragmentation , 1984 .

[24]  H. Kagan,et al.  Divalent lanthanide derivatives in organic synthesis. 1. Mild preparation of samarium iodide and ytterbium iodide and their use as reducing or coupling agents , 1980 .

[25]  A. Otaka,et al.  Development of new methodology for the synthesis of functionalized α-fluorophosphonates and its practical application to the preparation of phosphopeptide mimetics , 2000 .

[26]  N. Fujii,et al.  Determination of absolute configuration of the alkyl group at the α-position in the acyclic α-alkyl-(E)-β,γ-enoates by circular dichroism , 1990 .

[27]  P. Furet,et al.  Fluoroolefin dipeptide isosteres -II. , 1990 .

[28]  G. Bernardinelli,et al.  Enantioselective synthesis and absolute configuration of (−)-pulo'upone by asymmetric intramolecular diels-alder reaction , 1988 .

[29]  R. J. Abraham,et al.  A theoretical and crystallographic study of the geometries and conformations of fluoro-olefins as peptide analogues , 1986 .

[30]  P. A. Tardella Control of the alkylation of ketone enolates with tributyl tin chloride and triethyl aluminum , 1969 .