204443-54-9Relevant articles and documents
Enantioselective Synthesis of 3-Deoxy-(R)-sphingomyelin from (S)-1-(4′-Methoxyphenyl)glycerol
Byun, Hoe-Sup,Sadlofsky, Jason A.,Bittman, Robert
, p. 2560 - 2563 (1998)
(R)-3-Deoxysphingomyelin (2) was prepared from (S)-1-(4′-methoxyphenyl)-glycerol (3). The latter was converted into either p-methoxyphenyl (PMP) (S)-oxiranylmethyl ether (5) or (R)-1-(4′-methoxyphenyl)glycerol 2,3-cyclic sulfate (6). Opening of 5 with lithium pentadecyne in the presence of BF3·Et2O gave PMP (S)-2-hydroxy-4-octadecynyl ether (7) in 65percent yield. Alternatively, opening of cyclic sulfate 6 with excess lithium pentadecyne in the presence of catalytic cuprous iodide, followed by acidic workup, gave 7 in 90percent yield. After introduction of the amide group via azide displacement, reduction, and N-acylation, simultaneous reduction of the triple bond and deprotection of the PMP group by Birch reduction (Li, EtNH2) provided 3-deoxy-N-palmitoyl-(A)-ceramide (9). Finally, phosphitylation of 9, oxidation of the cyclic phosphite with bromine, followed by in situ ring opening gave a (2-bromoethyl)phosphate ester, which on quaternization with aqueous trimethylamine afforded 3-deoxy-N-palmitoyl-(R)-sphingomyelin (2) in 49percent overall yield from PMP (S)-2-hydroxy-4-octadecynyl ether (7).