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Synthesis 2010(5): 757-762  
DOI: 10.1055/s-0029-1219081
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Enantioselective Synthesis of Homosphingosine Derivatives from l-Aspartic Acid

Sami J. K. Sauerlanda, Joel A. Castillo-Meléndeza, Kalle Nättinenb, Kari Rissanenb, Ari M. P. Koskinen*a
a Department of Chemical Technology, Laboratory of Organic Chemistry, Helsinki University of Technology, P.O. Box 6100, 02015 Helsinki, Finland
Fax: +358(9)4512538; e-Mail: ari.koskinen@tkk.fi;
b X-ray crystallography; Nanoscience Center, Department of Chemistry, University of Jyväskylä, P.O. Box 35, 40014 Jyväskylä, Finland
Further Information

Publication History

Received 2 November 2009
Publication Date:
16 December 2009 (online)

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Abstract

The sterically demanding 9-phenylfluorenyl N-protection of a number of amino acids allows the formation of amino acid derived β-ketophosphonate reagents and their Horner-Wadsworth-Emmons olefination. In an attempt to develop a synthesis of d-erythro-homosphingosine in enantiopure form, we have shown that the reactivity of the intermediates is influenced by the distinctive conformational requirements of this large protecting group.

Key words

diastereoselectivity - enantioselectivity - sphingosine - ceramide

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12

X-ray crystallography was performed at the University of Jyväskylä with a Nonius Kappa CCD diffractometer. Crystal data for 10: Orthorhombic; P212121 (No. 19); a = 9.0028 (3) Å, b = 9.4284 (3) Å, c = 25.0491 (8) Å; R1 = 0.0453, wR2 = 0.0847 (I > 2σ). 12: Monoclinic; P21 (No. 4); a = 9.8177 (7) Å, b = 8.8352 (5) Å, c = 11.3458 (8) Å, β = 92.366 (3)˚; R1 = 0.0490, wR2 = 0.0955 (I > 2σ). 6a: Orthorhombic; P212121 (No. 19); a = 14.9329 (6) Å, b = 15.1590 (5) Å, c = 17.2261 (5) Å; R1 = 0.0573, wR2 = 0.0936 (I > 2σ). CCDC 255363-255365 contain the supplementary crystallographic data (excluding structure factors) for this paper. These data can be obtained online free of charge or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ UK [fax: (+44)1223336033; or deposit@ccdc.cam.ac.uk].

19

The stereochemistry was assigned based on analogy with previous reductions, as well as on the coupling constants for similar compounds; see, for example, ref. 8d.