(-)-(1R,2S)-肉豆蔻木脂素的不对称合成

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (9): 1780.

(-)-(1R,2S)-肉豆蔻木脂素的不对称合成

夏亚穆, 常亮

青岛科技大学化工学院, 青岛 266042

收稿日期:2009-12-11 出版日期:2010-09-10 发布日期:2010-09-10
通讯作者: 夏亚穆, 男, 博士, 副教授, 主要从事有机合成研究. E-mail: xiaym@qust.edu.cn
基金资助:
高等学校博士学科点专项科研基金(批准号: 20093719120004)、山东省泰山学者专项基金(批准号: 2005011036)和化学工程山东省强化建设学科开放基金资助.

Asymmetric Synthesis of (-)-(1R,2S)-Myrislignan

XIA Ya-Mu^* , CHANG Liang

College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

Received:2009-12-11 Online:2010-09-10 Published:2010-09-10
Contact: XIA Ya-Mu. E-mail: xiaym@qust.edu.cn
Supported by:
高等学校博士学科点专项科研基金(批准号: 20093719120004)、山东省泰山学者专项基金(批准号: 2005011036)和化学工程山东省强化建设学科开放基金资助.

摘要/Abstract

摘要： 报道了天然产物(-)-肉豆蔻木脂素的全合成. 以香草醛为起始原料, 经Wittig反应、LiAlH₄还原和Sharplass不对称双羟化等反应构建了苏式结构的中间体; 以焦性没食子酸为原料, 经Claisen重排反应制得另一种苯丙素片段; 2个中间体通过Mitsunobu反应, 缩合并使构型翻转, 得到赤式-(-)-肉豆蔻木脂素. 为赤式8-O-4′新木脂素的合成提供了一种新方法.

关键词: 不对称合成, 肉豆蔻木脂素, 新木脂素, Mitsunobu反应

Abstract: Natural product erythro-(-)-(1R,2S)-Myrislignan, which was firstly found in the seeds of nutmeg of the aril(mace) of Myristica fragrans Houtt(Myristicaceae) used as traditional Chinese medicine in China and Japan and it has attracted increasing interest because of its biological activities, was synthesized for the first time in high yields from vanillin. The synthesis was based on a unified synthetic strategy and involved Wittig reaction, LiAlH₄ reduction and Sharplass asymmetric dihydroxylation reaction to prepare a threo-intermediate of predictable stereochemistry. Then pyrogallic acid was employed as material to prepare the other phenylpropanoid unit by Claisen rearrangement reaction. The stereoselective coupling between the threo-intermediate and phenylpropanoid unit inverted the absolute configuration from threo- to erythro-isomer using the Mitsunobu reaction to give the target product. The route illustrates a new methodology for the synthesis of erythro-8-O-4′ neolignans.

Key words: Asymmetric synthesis, Myrislignan, Neolignan, Mitsunobu reaction

TrendMD:

夏亚穆, 常亮. (-)-(1R,2S)-肉豆蔻木脂素的不对称合成. 高等学校化学学报, 2010, 31(9): 1780.

XIA Ya-Mu* , CHANG Liang. Asymmetric Synthesis of (-)-(1R,2S)-Myrislignan. Chem. J. Chinese Universities, 2010, 31(9): 1780.

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