17 2,3-O-イソブロピリデン-D-グリセリン酸メチルを出発物質とするD-erythro-C_<18>-スフィンゴシンの合成(ポスター発表の部)

概要

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As one of the synthetic studies on complex carbohydrates, the formal synthesis of D-erythro-C_<18>-sphingosine (2), an essenstial constituent of sphingolipids, from methyl 2,3-O-isopropylidene-D-glycerate(1) are described. First, we studied the Horner-Wittig reaction of phosphonate 4, which was synthesized from dimethyl methylphosphonate and 1, and found the use of caesium carbonate as base in isopropyl alcohol effective to promote this reaction and to give (E)-olefin selectively. In this manner intermediate 6 was obtained in 85% yield. Next, we tried the stereoselective reduction of ketone 6 in tetrahydrofuran using several hydrides and found L-Selectride gave the desired syn-glycerol derivative(7a) in 90% d.e. stereoselectively. Finally, the deprotection of isopropylidene group of 7a and the following benzylidenation in general manner gave the benzylidene glycerol derivative (12), from which the synthesis of 2 have been reported. Thus, the formal synthesis of 2 was completed. Further the phosphonate 4 described herein is expected to be an efficient intermediate of other poly-functional natural products.
天然有機化合物討論会の論文
1988-09-26