35 海産エイコサノイドConstanolactone E及びBacillariolides I-IIIの全合成(口頭発表の部)
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A new method for synthesis of chiral cycloalkane derivatives was explored. The new method involves the formation of cycloalkane in a one-pot process using the anion of allyl phenyl sulfone and chiral epoxymesylate (Scheme 1). Total synthesis of marine eicosanoid constanolactone E and bacillariolides I-III was achieved using this new method. Constanolactone E (1), isolated from the marine red alga Constantinea simplex, is a cyclopropane-containing eicosanoid. Reaction of the lithio derivative of allyl phenyl sulfone with chiral epoxymesylate 2 gave cyclopropane 3 as a diastereomeric mixture at C-8 in a ratio of 8: 1 (Scheme 2). Cyclopropane 3 was converted to sulfone 5 via aldehyde 4. The Julia's olefination of sulfone 5 with aldehyde 6 afforded E-olefm 9. Following the selective deprotection of TBDMS ether in 9, hydroxymethyl group was converted to the methoxycarbonyl group. Deprotections of acetonide and TBDPS ether, and then lactonization completed the synthesis of constanolactone E (1). Bacillariolides I (11), II (12) and III (13), isolated from the marine diatom, Pseudo-nitzschia multiseries, are cyclopentane-containing structurally unique eicosanoids. Reaction of the lithio derivative of allyl phenyl sulfone with epoxymesylate 19, prepared from diol 14, gave cyclopentane 20 as the sole product (Scheme 3). Cyclopentane 20 was converted to lactone 21 by oxidation of terminal olefin, Jonens oxidation and removal of the phenylsulfonyl group. Deprotection of MPM ether in 21 afforded an alcohol, which was oxidized by the Swern procedure to give the aldehyde 22. Coupling reaction of the aldehyde 22 with Wittig reagent, prepared using phosphonium salt 23 afforded the (8Z,11Z,14Z,17Z)-tetraene. Finally, deprotection of MOM ether completed the synthesis of bacillariolide II (12). Bacillariolides I (11) and III (13) were synthesized from lactone 21 via epimerization of the C-7 position, respectively (Scheme 4).
- 天然有機化合物討論会の論文
- 1998-08-31
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