通过动力学拆分对棉铃象鼻虫聚集信息素的成分（+）-大香叶烯醇进行不对称合成。

An asymmetric synthesis of (+)-grandisol, a constituent of the aggregation pheromone of the cotton boll weevil, via a kinetic resolution.

作者信息

Hamon D P, Tuck K L

机构信息

The Department of Chemistry, The University of Adelaide, S.A. 5005, Australia.

出版信息

J Org Chem. 2000 Nov 17;65(23):7839-46. doi: 10.1021/jo000853+.

DOI:10.1021/jo000853+

PMID:11073589

Abstract

A novel approach to the asymmetric synthesis of (+)-grandisol, (1R, 2S)-isopropenyl-1-methylcyclobutaneethanol, involves the use of catalytic kinetic resolution of a primary allylic alcohol, [(1RS, 5SR)-5-methylbicyclo[3.2.0]hept-2-en-2-yl] methanol. The allylic alcohol is prepared in four steps from simple achiral materials involving the use of a modified Shapiro reaction. The resolved alcohol (95% ee) is then reduced in two steps to the corresponding methyl alkene, (1S,5R)-2,5-dimethylbicyclo[3.2.0]hept-2-ene. This alkene is converted to (+)-grandisol (95% ee), in three steps, by modified literature procedures.

摘要

一种用于不对称合成(+)-大根香叶醇，即(1R, 2S)-异丙烯基-1-甲基环丁烷乙醇的新方法，涉及对一种伯烯丙醇，即[(1RS, 5SR)-5-甲基双环[3.2.0]庚-2-烯-2-基]甲醇进行催化动力学拆分。该烯丙醇由简单的非手性原料通过四步反应制备，其中涉及使用改进的夏皮罗反应。拆分得到的醇（对映体过量值为95%）然后经过两步反应还原为相应的甲基烯烃，即(1S,5R)-2,5-二甲基双环[3.2.0]庚-2-烯。通过改进的文献方法，该烯烃经过三步反应转化为(+)-大根香叶醇（对映体过量值为95%）。