Diastereoselective Synthesis of (S)- and (R)-α-Phenylserine by a Sulfinimine-Mediated Strecker Reaction

Abstract

A straightforward and efficient diastereoselective synthesis of (S)- and (R)-α-phenylserine is reported. The key step involves an asymmetric Strecker reaction of a chiral N-sulfinyl ketimine, which was obtained from the commercially available 2-hydroxyacetophenone.

Key words

amino acids - asymmetric synthesis - imines - nitriles - nucleophilic addition

References

• 1a Cativiela C. Diaz-de-Villegas MD. Tetrahedron: Asymmetry  1998,  9:  3517 
• 1b Toniolo C. Crisma M. Formaggio F. Peggion C. Biopolymers  2001,  60:  396 
• 1c Ohfune Y. Shinada T. Bull. Chem. Soc. Jpn.  2003,  76:  1115 
• 2a Williams RM. Hendrix JA. Chem. Rev.  1992,  92:  889 
• 2b Duthaler RO. Tetrahedron  1994,  50:  1539 
• 2c Gröger H. Chem. Rev.  2003,  103:  2795 
• 3a Cogan DA. Liu G. Ellman JA. Tetrahedron  1999,  55:  8883 
• 3b Ellman JA. Owens TD. Tang TP. Acc. Chem. Res.  2002,  35:  984 
• 3c Zhou P. Chem B.-C. Davis FA. Tetrahedron  2004,  60:  8003 
• 4 Bloch R. Chem. Rev.  1998,  98:  1407 
• 5a Avenoza A. Cativiela C. Corzana F. Peregrina JM. Sucunza D. Zurbano MM. In Targets in Heterocyclic Systems   Attanasi OA. Spinelli D. Italian Society of Chemistry; Rome: 2002.  p.231-244  ; and references cited therein
• 5b Avenoza A. Busto JH. Corzana F. Peregrina JM. Sucunza D. Zurbano MM. Tetrahedron: Asymmetry  2004,  15:  131 
• 5c Avenoza A. Busto JH. Corzana F. Peregrina JM. Sucunza D. Zurbano MM. Tetrahedron: Asymmetry  2004,  15:  719 
• 5d Avenoza A. Busto JH. Corzana F. Jiménez-Osés G. Peregrina JM. Chem. Commun.  2004,  980 
• 6 Olma A. Pol. J. Chem.  1996,  70:  1442 
• 7a Marco JA. Carda M. Murga J. González F. Falomir E. Tetrahedron Lett.  1997,  38:  1841 
• 7b Carda M. Murga J. Rodríguez S. González F. Castillo E. Marco JA. Tetrahedron: Asymmetry  1998,  9:  1703 
• 8 Liu G. Cogan DA. Owens TD. Tang TP. Ellman JA. J. Org. Chem.  1999,  64:  1278 
• 9 Davis FA. Lee S. Zhang H. Fanelli DL. J. Org. Chem.  2000,  65:  8704 
• 11 Tang TP. Volkman SK. Ellman JA. J. Org. Chem.  2001,  66:  8772 
• 12a

  Crystal data of compound 1: C₃₉H₅₄N₆O₆S₃, M _w = 799.06, colorless prism of 0.30 × 0.12 × 0.10 mm, T = 173 K, orthorhombic, space group P 2₁ 2₁ 2₁, Z = 4, a = 12.5430 (10) Å, b = 18.4770 (10) Å, c = 18.5730 (10) Å, α = 90.000(10), β = 90.000(10), γ = 90.000(10)°, V = 4304.4 (5) ų, d _calc = 1.233 g cm^-3, F(000) = 1704, λ = 0.71073 Å (Mo, Kα), µ = 0.086 mm^-1, Nonius kappa CCD diffractometer, θ range 1.55-25.01°, 7270 collected reflections, 7241 unique, full-matrix least-squares (SHELXL97^12b), R1 = 0.0586, wR2 = 0.1142, (R1 = 0.1026, wR2 = 0.1304 all data), goodness of fit = 1.029, residual electron density between 0.254 and -0.263 e Å^-3. Hydrogen atoms fitted at theoretical positions. Further details on the crystal structure are available on request from Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, UK on quoting the depository number 246445.

• 12b Sheldrick GM. SHELXL97, Program for the Refinement of Crystal Structures   University of Göttingen; Germany: 1997. 

10

HPLC conditions: Lichrospher Si (5 µm, 250 × 4.6 mm), hexane-MTBE = 70:30, 0.6 mL/min, 265 nm, 25 °C.