18 鎖状立体制御によるsyn-1,3-ポリオール合成と天然物合成への応用(ポスター発表の部)

概要

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In connection with our stereochemical study of sporaviridin, a polyol macrolide antibiotic, we succeeded in developing a convergent and general protocol for syn-1,3-polyol synthesis, which is extendable to higher homologues of this series by repetition. Our synthesis started with the coupling reaction of the chiral building block (9) and the epoxide (10) to give the hydroxy ketone (12) after dethioacetalization. The highly syn-diastereoselective reduction of 12 was achieved using LiAlH_4-LiI, giving a syn-1,3-diol derivative (13). The LiAlH_4-LiI reduction is a useful method for preparing syn-1,3-diols from β-alkoxy and β-alkoxy-β'-hydroxy ketones. The selectivity of this reduction is syn:anti =95:5 (see Table I and II). A second coupling of 17 and 9, followed by dethioacetalization, syn-selective reduction of 19 with LiAlH_4-LiI, and deprotection of 20 gave all-syn-heptol derivative (22). The success of the present convergent synthesis is particulary owed to the developments of a new chiral building block (9) and a highly syn-selective LiAlH_4-LiI reduction method. Applications of this new method were demonstrated in the synthses of the attractant (27) of Ambrosia beetle and (-)- and (+)-tarchonanthuslactone (32), which contain syn-1,3-polyol subunits.
天然有機化合物討論会の論文
1988-09-26