A highly stereocontrolled formal total synthesis of (±)- and of (-)-grandisol by 1,4-conjugated addition of organocopper reagents to cyclobutylidene derivatives
A highly stereocontrolled formal total synthesis of (±)- and of (-)-grandisol by 1,4-conjugated addition of organocopper reagents to cyclobutylidene derivatives
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DOI：
10.1016/j.tet.2007.03.134
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发表时间：
2007-06-04
期刊：
影响因子：
2.1
通讯作者：
Spiga, Marco
中科院分区：
文献类型：
--
作者：
Bernard, Angela M.;Frongia, Angelo;Spiga, Marco
从合适的环丙烷出发，合成了外消旋格兰地醇和对映体(-)格兰地醇。格拉迪索前体的外消旋合成分五步完成。该信息素的手性非外消旋前体(1S，2S，2‘R)-cis以对映体环丁酮(R，S)为原料，经10步反应合成，总收率45%。关键的立体定义步骤是将二甲基铜酸锂加到手性α，β-不饱和环丁叉基衍生物中。(C)2007爱思唯尔有限公司。保留所有权利。
Starting from suitable cyclopropanes, a formal total synthesis of racemic grandisol and of the enantiopure (-)-grandisol is presented. The racemic synthesis of the grandisol precursor was accomplished in five steps. The synthesis of the chiral non-racemic precursor (1S,2S,2 ' R)-cis of this pheromone was realized in 10 steps, with an overall yield of 45%, using the enantiopure cyclobutanone (R,S), previously obtained by ring expansion of an optically pure oxaspiropentane. The key stereodefining step was the addition of lithium dimethylcuprate to a chiral alpha,beta-unsaturated cyclobutylidene carbonyl derivative. (c) 2007 Elsevier Ltd. All rights reserved.