B. Kratzer et Rr. Schmidt, EFFICIENT SYNTHESIS OF SPHINGOSINE-1-PHOSPHATE, CERAMIDE-1-PHOSPHATE,LYSOSPHINGOMYELIN, AND SPHINGOMYELIN, Liebigs Annalen, (6), 1995, pp. 957-963
Readily available D-erythro-azidosphingosine is transformed into 3-O-s
ilyl-protected derivative 6. Reduction of the azido group afforded 3-O
-silyl-protected sphingosine 7 which was either converted into N-Fmoc-
protected derivative 8 or via N-acylation into ceramide derivatives 16
and 17, respectively. Treatment of 6, 8, and 16 with bis(2-cyanoethox
y)(diisopropylamino)phosphane as monofunctional phosphitylating agent,
subsequent oxidation and then removal of the protective groups furnis
hed azidosphingosine-1-phosphate (11), sphingosine-1-phosphate (2), an
d ceramide-1-phosphate (4), respectively. Treatment of 8 and 17 with b
is(diisopropylamino) (2-cyanoethoxy)phosphane as bifunctional phosphit
ylating agent and then with choline afforded after oxidation and subse
quent deprotection lysosphingomyelin (3) and sphingomeylin (1), respec
tively in high overall yields. All final products are stereochemically
pure and possess D-erythro configuration in the sphingosine moiety.