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.

dihydroxylation - diastereoselectivity - stereoselective synthesis - sphingolipids - amino alcohols

References

For an excellent overview of sphingolipid functions, see:

<A NAME="RT08102SS-1A">1a</A> Merrill AH. Sweeley CC. Biochemistry of Lipids, Lipoproteins and Membranes   Vance DE. Vance JE. Elsevier; Amsterdam: 1996.  Chap. 12. p.309 

<A NAME="RT08102SS-1B">1b</A> Vankar YD. Schmidt RR. Chem. Soc. Rev.  2000,  29:  201 

<A NAME="RT08102SS-2">2</A> Okabe K. Keeman RW. Schmidt G. Biochem. Biophys. Res. Commun.  1968,  31:  137 

<A NAME="RT08102SS-3">3</A> Takamatsu K. Mikami M. Kikuchi K. Nozawa S. Iwamori M. Biochim. Biophys. Acta  1992,  1165:  177 

<A NAME="RT08102SS-4">4</A> Barenholz Y. Gatt S. Biochem. Biophys. Res. Commun.  1967,  27:  319 

<A NAME="RT08102SS-5A">5a</A> Wertz PW. Miethke MC. Long SA. Stauss JS. Downing DT. J. Invest. Dertmatol.  1985,  84:  410 

<A NAME="RT08102SS-5B">5b</A> Schmidt RR. In Liposome Dermatics   Braun-Falco O. Corting HC. Maibach HI. Springer-Verlag; Berlin: 1992.  p.44-56  

<A NAME="RT08102SS-6A">6a</A> Karlsson KA. Samuelsson BE. Steen GO. Acta Chem. Scand.  1968,  22:  136 

<A NAME="RT08102SS-6B">6b</A> Karlsson KA. Acta Chem. Scand.  1964,  18:  2395 

<A NAME="RT08102SS-7">7</A> Vance DE. Sweeley CC. J. Lipid Res.  1967,  8:  621 

<A NAME="RT08102SS-8">8</A> Zellner J. Monatsh. Chem.  1911,  32:  133 

<A NAME="RT08102SS-9A">9a</A> Oda T. J. Pharm. Soc. Jpn.  1952,  72:  142 

<A NAME="RT08102SS-9B">9b</A> Carter HE. Hendrickson HS. Biochemistry  1963,  2:  389 

<A NAME="RT08102SS-10A">10a</A> Dickson RC. Nagiec EE. Skrzypek M. Tillman P. Wells GB. Lester RL. J. Biol. Chem.  1997,  272:  30196 

<A NAME="RT08102SS-10B">10b</A> Schneiter R. Bioessays  1999,  21:  1004 

<A NAME="RT08102SS-10C">10c</A> Kobayashi E. Motoki K. Yamaguchi Y. Uchida T. Fukushima H. Koezuka Y. Oncol. Res.  1995,  7:  529 

<A NAME="RT08102SS-11">11</A> Martin C. Prunck W. Bortolussi M. Bloch R. Tetrahedron: Asymmetry  2000,  11:  1585 ; and references cited therein

<A NAME="RT08102SS-12">12</A> Sisido K. Tamura H. Kobata H. Takagisi M. Isida T. J. Org. Chem.  1970,  35:  350 

<A NAME="RT08102SS-13A">13a</A> Schmidt RR. Maier T. Carbohydr. Res.  1988,  174:  169 

<A NAME="RT08102SS-13B">13b</A> Sugiyama S. Honda M. Komori T. Liebigs Ann. Chem.  1990,  1069 

<A NAME="RT08102SS-13C">13c</A> Li YL. Mao XH. Wu YL. J. Chem. Soc., Perkin Trans. 1  1995,  1559 

<A NAME="RT08102SS-13D">13d</A> Nakamura T. Shiozaki M. Tetrahedron Lett.  1999,  40:  9063 

<A NAME="RT08102SS-13E">13e</A> Shirota O. Nakanishi K. Berova N. Tetrahedron  1999,  55:  13643 

<A NAME="RT08102SS-13F">13f</A> He L. Byun H.-S. Bittman R. J. Org. Chem.  2000,  65:  7618 

<A NAME="RT08102SS-14">14</A> Fernandes RA. Kumar P. Tetrahedron Lett.  2000,  41:  10309 

<A NAME="RT08102SS-15A">15a</A> Becker H. Sharpless KB. Angew. Chem., Int. Ed. Engl.  1996,  35:  448 

<A NAME="RT08102SS-15B">15b</A> Kolb HC. VanNiewenhze MS. Sharpless KB. Chem. Rev.  1994,  94:  2483 

<A NAME="RT08102SS-15C">15c</A> 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 

<A NAME="RT08102SS-16A">16a</A> Schroeder M. Chem. Rev.  1980,  80:  187 

<A NAME="RT08102SS-16B">16b</A> Hanson RM. Chem. Rev.  1991,  91:  437 

<A NAME="RT08102SS-17">17</A> Ireland RE. Wipf P. Roper TD. J. Org. Chem.  1990,  55:  2284 

<A NAME="RT08102SS-18">18</A> Hoffmann RW. Schlapbach A. Tetrahedron Lett.  1993,  34:  7903 

<A NAME="RT08102SS-19">19</A> Rickards RW. Thomas RD. Tetrahedron Lett.  1993,  34:  8369 

<A NAME="RT08102SS-20">20</A> Barvin MR. Greenberg MM. J. Org. Chem.  1993,  58:  6151 

<A NAME="RT08102SS-21">21</A> Kim N.-S. Choi J.-R. Cha JK. J. Org. Chem.  1993,  58:  7096 

<A NAME="RT08102SS-22A">22a</A> Pais GCG. Fernandes RA. Kumar P. Tetrahedron  1999,  55:  13445 

<A NAME="RT08102SS-22B">22b</A> Fernandes RA. Kumar P. Tetrahedron: Asymmetry  1999,  10:  4349 

<A NAME="RT08102SS-22C">22c</A> Fernandes RA. Kumar P. Eur. J. Org. Chem.  2002,  2921 

<A NAME="RT08102SS-22D">22d</A> Fernandes RA. Kumar P. Tetrahedron: Asymmetry  1999,  10:  4797 

<A NAME="RT08102SS-22E">22e</A> Fernandes RA. Kumar P. Eur. J. Org. Chem.  2000,  3447 

<A NAME="RT08102SS-22F">22f</A> Pandey RK. Fernandes RA. Kumar P. Tetrahedron Lett.  2002,  43:  4425 

<A NAME="RT08102SS-22G">22g</A> Fernandes RA. Bodas MS. Kumar P. Tetrahedron  2002,  58:  1223 

<A NAME="RT08102SS-22H">22h</A> Fernandes RA. Kumar P. Tetrahedron  2002,  58:  6685 

<A NAME="RT08102SS-23">23</A>

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.

<A NAME="RT08102SS-24">24</A>

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

For examples of double diastereoselective asymmetric dihydroxylation of chiral monosubstituted olefins, see:

<A NAME="RT08102SS-25A">25a</A> Jirousek MR. Cheung AW.-H. Babine RE. Sass PM. Schow SR. Wick MM. Tetrahedron Lett.  1993,  34:  3671 

<A NAME="RT08102SS-25B">25b</A> Sinha SC. Keinan E. J. Org. Chem.  1994,  59:  949 

<A NAME="RT08102SS-25C">25c</A> Gurjar MK. Mainkar AS. Syamala M. Tetrahedron: Asymmetry  1993,  4:  2343 

<A NAME="RT08102SS-26">26</A> Taber DF. J. Org. Chem.  1982,  47:  1351