Chemoenzymatic synthesis of all four stereoisomers of sphingosine from chlorobenzene: Glycosphingolipid precursors

被引:66
作者
Nugent, TC [1 ]
Hudlicky, T [1 ]
机构
[1] Univ Florida, Dept Chem, Gainesville, FL 32611 USA
关键词
D O I
10.1021/jo971335a
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Advantageous use of homochiral cyclohexadiene-cis-1,2-diol 2, available by means of biocatalytic oxidation of chlorobenzene with toluene dioxygenase, has enabled the synthesis of all four enantiomerically pure C-18-sphingosines 1. The four requisite diastereomers of azido alcohols 4a-d were accessed by regioselective opening of epoxides 7 and 8 with either azide or halide ions. The configuration of C4 and C5 in azides 4 defines the stereochemistry of the incipient sphingosine chain, liberated from 4 by the oxidative cleavage of the C1-C6 olefin. For L-threo-sphingosine (1b), lactol 20b generated by this cleavage was concerted by periodate oxidation to azido deoxy L-threose 22b, which gave 1b upon Wittig olefination and reduction. Similarly, D-erythro-sphingosine (1a) and L-erythro-sphingosine (1c) were generated from 4a,c, respectively. The last sphingosine (1d) was synthesized from the silyl-protected azido alcohol 29d. Subsequent transformations provided silyl-protected azido deoxy D-threose 32d, which upon Wittig olefination and reduction gave D-threo-sphingosine (1d). Experimental and spectral data are provided for all new compounds.
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页码:510 / 520
页数:11
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