Diastereoselective Hydrolysis of α,γ-Substituted γ-Sultones in the Asymmetric Synthesis of γ-Hydroxy Sulfonates

Abstract

The hydrolysis of enantiopure α,γ-substituted γ-sultones with water under mild conditions leads to α,γ-substituted γ-hydroxy methyl sulfonates in very good yields and excellent diastereo- and enantiomeric excesses (de, ee ≥ 98%). The reaction proceeds via a S_N2 mechanism with inversion of configuration at the attacked γ-carbon atom whose absolute configuration was established by X-ray crystallography.

Key words

sultones - sulfonates - asymmetric synthesis - hydrolysis - ring-opening

References

• 1 Kalir A. Kalir HH. In The Chemistry of Sulfonic Acids, Esters and their Derivatives   Patai S. Rappoport Z. Wiley; Chichester, New York: 1991.  Chap. 18.
• 2 Traynor SG. Kane BJ. Betkouski MF. Hirschy LM. J. Org. Chem.  1979,  44:  1557 
• 3 Kitamura M. Yoshimura M. Kanda N. Noyori R. Tetrahedron  1999,  55:  8769 
• 4a Higashiura K. Morino H. Matsuura H. Toyomaki Y. Ienaga K. J. Chem. Soc., Perkin Trans. 1  1989,  1479 
• 4b Higashiura K. Ienaga K. J. Org. Chem.  1992,  57:  764 
• 5 Xu J. Tetrahedron: Asymmetry  2002,  13:  1129 
• For reviews on sultone chemistry see:
• 6a Mustafa A. Chem. Rev.  1954,  57:  195 
• 6b Fischer RF. Ind. Eng. Chem.  1964,  56:  41 
• 6c Roberts DW. Williams DL. Tetrahedron  1987,  43:  1027 
• 6d Buglass AJ. Tillet JG. In The Chemistry of Sulfonic Acids, Esters and Their Derivatives   Patai S. Rappoport Z. Wiley; Chichester, New York: 1991.  Chap. 19.
• 6e Metz P. J. Prakt. Chem.  1998,  340:  1 
• 7 Bordwell FG. Osborne CE. Chapman RD. J. Am. Chem. Soc.  1959,  81:  2698 
• 8 Mori A. Nagayama M. Mandai H. Bull. Chem. Soc. Jpn.  1971,  44:  1669 
• 9 Nilsson T. Ph.D. Thesis   University of Lund; Sweden: 1946. 
• 10 Kaiser C. Püschel F. Chem. Ber.  1964,  97:  2926 
• 11a Enders D. Vignola N. Berner OM. Angew. Chem. Int. Ed.  2002,  41:  109 ; Angew. Chem. 2002, 114, 116
• 11b Enders D. Berner OM. Vignola N. Chem. Commun.  2001,  2498 
• 11c Enders D. Berner OM. Vignola N. Harnying W. Synthesis  2002,  1945 
• 12a Enders D. Harnying W. Vignola N. Synlett  2002,  1727 
• 12b Enders D. Harnying W. Vignola N. Eur. J. Org. Chem.  2003,  20:  3939 
• 15 Flack HD. Acta Crystallogr., Sect. A  1983,  39:  876 

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X-ray Crystallographic Study of 4a: The compound (C₁₀H₁₆O_5.5SNa: M_r = 279.29) crystallizes in monoclinic space group C2 (Nr. 5) with cell dimensions of a = 14.019(3), b = 5.6250(11), c = 17.061(3) Å, and β = 110.097(3)º. A cell volume of V = 1263.4(4) ų and Z = 4 result in a calculated density of ρ_calcd = 1.468 gcm^-3. 16500 reflections have been collected in the ω mode at T = 298 K on an Bruker SMART APEX CCD diffractometer employing MoK_α-radiation (λ = 0.71073 Å). Data collection covered the range -18 ≤ h £ 18, -7 £ k £ 7, and -22 £ l £ 22 up to θ_max = 28.29º; absorption correction with SADABS (µ = 0.301mm^-1). The structure has been solved by direct methods as implemented in the Xtal3.7 suite of crystallographic routines [14] where GENSIN has been used to generate the structure-invariant relationships and GENTAN for the general tangent phasing procedure. 1682 observed reflections [I>2σ(I)] have been included in the final full-matrix least-squares refinement on F involving 159 parameters and converging at R(R _w ) = 0.031 (0.041, w = 1/[σ²(F) + 0.0004F²]), S = 1.454, and a residual electron density of -0.17/0.33 eÅ^-3. The absolute configuration has been determined using Flack’s method and a data set collected using CuK_α radiation. X_abs = -0.022(55) [15] for the structure shown in Figure [1] . The hydrogen positions have been calculated in idealized positions. Their Us have been fixed at 1.5 times U of the relevant heavy atom, and no hydrogen parameters have been refined. The asymmetric unit contains 1.5 water molecules which explains deviations between the crystallographic and chemical formulae and densities. The crystal structure of 4a has been deposited as supplementary publication no. CCDC 227543 at the Cambridge Crystallographic Data Centre. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: [phone]; e-mail: [e-mail], or http//www.ccdc.cam.ac.uk).

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Hall, S. R.; du Boulay, D. J.; Olthof-Hazekamp, R. Xtal3.7 System, University of Western Australia, 2000.