3 海産ジテルペノイドClaenoneの全合成(口頭発表の部)
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Claenone (1) is a dolabellane type of marine diterpenoid, isolated from the Okinawan soft coral Clavularia sp., showing potent antiproliferative activity. We describe herein a total synthesis of claenone (1). Syntheses of dolabellatrienone and dolabellatrienol are also described. The sequential Michael reaction of kinetic enolate of cyclopentenone derivative 2 with optically active α,β-unsaturated ester 3 afforded bicyclo[2.2.1]heptane derivative 4a and 4b (4a: 4b=5.3: 1). Ketone 4a was converted to β-hydroxyketone 8 in several steps. Retro-aldol reaction of 8 was successfully carried out by treatment of NaH in the presence of 15-crown-5 to afford diketone 9, which was then converted to tetrasubstituted cyclopentane derivative 13 (Scheme 1). Reaction of the lithio derivative of sulfone 13 with allylic bromide 16, prepared from hydroxyacetone, gave 17. Stepwise elongation of the upper side chain in 17 leading to allylic alcohol 23 was effected through 20 and 21. Asymmetric epoxidation of allylic alcohol 23, followed by mesylation gave epoxymesylate 24. The cyclization of epoxymesylate 24 was carried out by treatment with KHMDS to afford 25. Sulfone 25 was converted to allylic alcohol 27 in the following steps: 1) hydrolysis of ketal, 2) isomerization of olefine, 3) methylation of ketone, and 4) removal of the phenylsulfonyl group. Finally, allylic alcohol 27 was treated with PDC to complete the synthesis of claenone (1) (Scheme 3). Dolabellatrienone was synthesized from the synthetic intermediate 23, through dolabellatrienol (Scheme 4).
- 天然有機化合物討論会の論文
- 1997-07-20
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