143615-68-3Relevant academic research and scientific papers
Chemoenzymatic Synthesis of All Four Stereoisomers of Sphingosine from Chlorobenzene: Glycosphingolipid Precursors
Nugent, Thomas C.,Hudlicky, Tomas
, p. 510 - 520 (2007/10/03)
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 C18-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-thereo-sphingosine (1b), lactol 20b generated by this cleavage was converted by periodate oxidation to azido deoxy L-threose 22b, which gave 1b upon Wittig olefination and reduction. Similarly, D-erythrosphingosine (1a) and L-erythro-sphingosine (1c) were generated from 4a,c, respectively. The last sphingosine (Id) was synthesized from the silyl-protected azido alcohol 29d. Subsequent transformations provided silyl-protected azido deoxy D-threose 32d, which upon Wittig olefmation and reduction gave D-threo-sphingosine (1d). Experimental and spectral data are provided for all new compounds.
Syntheses of two pairs of enantiomeric C18-sphingosines and a palmitoyl analogue of gaucher spleen glucocerebroside
Shibuya,Kawashima,Narita,Ikeda,Kitagawa
, p. 1154 - 1165 (2007/10/02)
Sixteen kinds of chiral C4-epoxides [(-)-10a-d,(+)-10a-d,(-)-11a-d,(+)-11a-d], which are synthons in our synthetic strategy for complex lipids, have been prepared from (2Z)-2-butene-1,4-diol (6) by employing a Sharpless asymmetric epoxidation. By using the chiral C4-epoxides [(+)-10a,(-)-10a,(-)-11a,(+)-11a] as starting compounds, two pairs of enantiomeric (D-erythro, L-erythro, D-threo, and L-threo)-C18-sphingosines (1, 2, 3, 4) have been synthesized via a regioselective ring-opening of the epoxide ring with azide anion followed by reduction of the azide group to an amino group and a Wittig reaction. Furthermore, D-erythro-C18-sphingosine (1) has been converted to a palmitoyl analogue (5a) of Gaucher spleen glucocerebroside (5) through a reaction pathway including successive condensations with palmitic acid and D-glucose.
Synthesis of two pairs of enantiomeric C18-sphingosines
Shibuya,Kawashima,Ikeda,Kitagawa
, p. 7205 - 7208 (2007/10/02)
Two pairs of enantiomeric (D-erythro, L-erythro, D-threo, L-threo) C18-sphingosines have been synthesized from Z-butene-1,4-diol utilizing Sharpless asymmetric epoxidation and a regiospecific ring-opening reaction of the resulting C4-chiral epoxide with an azide anion.
A novel, efficient synthesis of (±)-erythro-sphingosine
Cardillo,Orena,Sandri,Tomasini
, p. 917 - 922 (2007/10/02)
A stereoselective synthesis of (±)-erythro-sphingosine triacetate (1) is described. The key reaction that determines the right stereochemistry is the iodocyclization of 1-trichloroacetimido-(2E,4E)-octadecadiene (5). The 4,5-dihydro-1,3-oxazine (6) through cleavage with HCl and treatment with Amberlyst A 26 in the AcO- form, followed by full acetylation, affords (1) in good yield.
