海産オキシリピンの全合成研究

抄録

A new method for synthesis of cycloalkane derivatives was explored. The new method involves the formation of cycloalkane derivative in a one-pot process using the anion of allyl phenyl sulfone and epoxymesylate. Total synthesis of marine oxylipin constanolactone E and bacillariolides I-IIIwas achieved applying this new method.
Constanolactone E, isolated from the marine red alga Constantinea simplex, is a cyclopropanecontaining oxylipin. Reaction of the lithio derivative of allyl phenyl sulfone with chiral epoxymesylate gave cyclopropane derivative. Cyclopropane derivative was converted to alkyl sulfone, corresponding to C1-C9 segment. Aldehyde corresponding to C10-C20 segment was synthesized from 2-deoxy-D-ribose. Coupling reaction of two segments completed the total synthesis of constanolactone E.
Bacillariolides I, II and III, isolated from the marine diatom, Pseado-nitzschia multiseries, are cyclopentane-containing structurally unique oxylipins. Reaction of the lithio derivative of allyl phenyl sulfone with epoxymesylate gave cyclopentane derivative. Cyclopentane derivative was converted to the aldehyde corresponding to C1-C8 segment. Coupling reaction of the aldehyde with Wittig reagent corresponding to C9-C20 segment completed the total synthesis of bacillariolide II. Bacillariolides I and III were synthesized from the cyclopentane derivative via epimerization of the C-7 position, respectively.