110(P44) フェノール性オキシムの不斉酸化的閉環反応 : スピロイソオキサゾリン環を有する海洋産天然物の合成研究(ポスター発表の部)
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The oxidative cyclization of o-phenolic oxime-acid derivatives has provided a powerful method for the construction of the spiroisoxazoline ring system. The isolation and structure determination of several bromotyrosine derived natural marine metabolites containing the spirocyclohexadienylisoxazoline moiety have been reported, and the racemic syntheses by way of the oxidative cyclization of an o-phenolic oxime-ester (±)-14 has been demonstrated. Control of absolute stereochemistry in the formation of spiroisoxazoline ring system is important for the synthesis of these natural products, however, there is no method for the enantiomerically enriched spiroisoxazoline 14. We describe herein the first example of the synthesis of enantiomerically enriched spiroisoxazoline-ester (-)-14 by the oxidative cyclization of o-phenolic oxime-ester 1b using the novel chiral tertiary alcohol 5 as chiral auxiliary and synthesis of (+)-aerothionin. The reaction of o-phenolic oxime-ester 1b with iodosylbenzene (PhIO) and camphorsulfonic acid (CSA) in dichloromethane at -78℃ proceeded smoothly to afford spiroisoxazoline 2b in 83% yield. As expected, the removal of chiral auxiliary of spiroisoxazoline 2b was accomplished by treatment with TFA in CH2_Cl_2 at room temperature for 1 h. Methylation (MeOH, DCC, DMAP, 30min) was carried out to give methyl ester (-)-14 having the S configuration in 75% e.e. (71% chemical yield). The absolute configuration of (-)-14 (84% e.e.) was determined by the synthesis of natural marine product, (+)-aerothionin. According to the Yamamura's method, optically active spiroisoxazoline-ester (-)-14 was reduced with Zn(BH_4)2, followed by treatment with butanediamine to afford (+)-aerothionin having the S-configuration.
- 天然有機化合物討論会の論文
- 1996-09-02
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