Enantioselective Syntheses of xylo-C₁₈-Phytosphingosines using Double Stereodifferentiation

Abstract

The concept of double stereodifferentiation in Sharpless asymmetric dihydroxylation has been studied and the results obtained are applied to the diastereoselective syntheses of xylo-isomers of C₁₈-phytosphingosine. The diastereomeric mixture obtained could be separated by column chromatography. Thus, the l-xylo-(2R,3S,4S)-C₁₈- and d-xylo-(2S,3R,4R)-C₁₈-phytosphing­osines as their tetraacetate derivatives were synthesized in dia­stereomerically pure form.

Key words

dihydroxylation - diastereoselectivity - stereoselective synthesis - sphingolipids - amino alcohols

References

• For an excellent overview of sphingolipid functions, see:
• 1a Merrill AH. Sweeley CC. Biochemistry of Lipids, Lipoproteins and Membranes   Vance DE. Vance JE. Elsevier; Amsterdam: 1996.  Chap. 12. p.309 
• 1b Vankar YD. Schmidt RR. Chem. Soc. Rev.  2000,  29:  201 
• 2 Okabe K. Keeman RW. Schmidt G. Biochem. Biophys. Res. Commun.  1968,  31:  137 
• 3 Takamatsu K. Mikami M. Kikuchi K. Nozawa S. Iwamori M. Biochim. Biophys. Acta  1992,  1165:  177 
• 4 Barenholz Y. Gatt S. Biochem. Biophys. Res. Commun.  1967,  27:  319 
• 5a Wertz PW. Miethke MC. Long SA. Stauss JS. Downing DT. J. Invest. Dertmatol.  1985,  84:  410 
• 5b Schmidt RR. In Liposome Dermatics   Braun-Falco O. Corting HC. Maibach HI. Springer-Verlag; Berlin: 1992.  p.44-56  
• 6a Karlsson KA. Samuelsson BE. Steen GO. Acta Chem. Scand.  1968,  22:  136 
• 6b Karlsson KA. Acta Chem. Scand.  1964,  18:  2395 
• 7 Vance DE. Sweeley CC. J. Lipid Res.  1967,  8:  621 
• 8 Zellner J. Monatsh. Chem.  1911,  32:  133 
• 9a Oda T. J. Pharm. Soc. Jpn.  1952,  72:  142 
• 9b Carter HE. Hendrickson HS. Biochemistry  1963,  2:  389 
• 10a Dickson RC. Nagiec EE. Skrzypek M. Tillman P. Wells GB. Lester RL. J. Biol. Chem.  1997,  272:  30196 
• 10b Schneiter R. Bioessays  1999,  21:  1004 
• 10c Kobayashi E. Motoki K. Yamaguchi Y. Uchida T. Fukushima H. Koezuka Y. Oncol. Res.  1995,  7:  529 
• 11 Martin C. Prunck W. Bortolussi M. Bloch R. Tetrahedron: Asymmetry  2000,  11:  1585 ; and references cited therein
• 12 Sisido K. Tamura H. Kobata H. Takagisi M. Isida T. J. Org. Chem.  1970,  35:  350 
• 13a Schmidt RR. Maier T. Carbohydr. Res.  1988,  174:  169 
• 13b Sugiyama S. Honda M. Komori T. Liebigs Ann. Chem.  1990,  1069 
• 13c Li YL. Mao XH. Wu YL. J. Chem. Soc., Perkin Trans. 1  1995,  1559 
• 13d Nakamura T. Shiozaki M. Tetrahedron Lett.  1999,  40:  9063 
• 13e Shirota O. Nakanishi K. Berova N. Tetrahedron  1999,  55:  13643 
• 13f He L. Byun H.-S. Bittman R. J. Org. Chem.  2000,  65:  7618 
• 14 Fernandes RA. Kumar P. Tetrahedron Lett.  2000,  41:  10309 
• 15a Becker H. Sharpless KB. Angew. Chem., Int. Ed. Engl.  1996,  35:  448 
• 15b Kolb HC. VanNiewenhze MS. Sharpless KB. Chem. Rev.  1994,  94:  2483 
• 15c Sharpless KB. Amberg W. Bennani YL. Crispino GA. Hartung J. Jeong KS. Kwong H.-L. Morikawa K. Wang Z.-M. Xu D. Zhang X.-L. J. Org. Chem.  1992,  57:  2768 
• 16a Schroeder M. Chem. Rev.  1980,  80:  187 
• 16b Hanson RM. Chem. Rev.  1991,  91:  437 
• 17 Ireland RE. Wipf P. Roper TD. J. Org. Chem.  1990,  55:  2284 
• 18 Hoffmann RW. Schlapbach A. Tetrahedron Lett.  1993,  34:  7903 
• 19 Rickards RW. Thomas RD. Tetrahedron Lett.  1993,  34:  8369 
• 20 Barvin MR. Greenberg MM. J. Org. Chem.  1993,  58:  6151 
• 21 Kim N.-S. Choi J.-R. Cha JK. J. Org. Chem.  1993,  58:  7096 
• 22a Pais GCG. Fernandes RA. Kumar P. Tetrahedron  1999,  55:  13445 
• 22b Fernandes RA. Kumar P. Tetrahedron: Asymmetry  1999,  10:  4349 
• 22c Fernandes RA. Kumar P. Eur. J. Org. Chem.  2002,  2921 
• 22d Fernandes RA. Kumar P. Tetrahedron: Asymmetry  1999,  10:  4797 
• 22e Fernandes RA. Kumar P. Eur. J. Org. Chem.  2000,  3447 
• 22f Pandey RK. Fernandes RA. Kumar P. Tetrahedron Lett.  2002,  43:  4425 
• 22g Fernandes RA. Bodas MS. Kumar P. Tetrahedron  2002,  58:  1223 
• 22h Fernandes RA. Kumar P. Tetrahedron  2002,  58:  6685 
• For examples of double diastereoselective asymmetric dihydroxylation of chiral monosubstituted olefins, see:
• 25a Jirousek MR. Cheung AW.-H. Babine RE. Sass PM. Schow SR. Wick MM. Tetrahedron Lett.  1993,  34:  3671 
• 25b Sinha SC. Keinan E. J. Org. Chem.  1994,  59:  949 
• 25c Gurjar MK. Mainkar AS. Syamala M. Tetrahedron: Asymmetry  1993,  4:  2343 
• 26 Taber DF. J. Org. Chem.  1982,  47:  1351 

23

The enantiomeric excess of the corresponding dibenzoate was determined by HPLC using Lichrocart 250-4 (4 mm ID × 25 cm) HPLC-Cartridge (R. R.-Whelk-01), 10% i-PrOH in hexane, 1 mL/min.

24

The diastereomeric ratio was determined by ¹H NMR and ¹³C NMR spectroscopy.