Institut für Organische Chemie und Biochemie, Freiburg Institute for Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg, Alberstr. 21, 79104 Freiburg, Germany.
J Org Chem. 2010 Jul 2;75(13):4424-33. doi: 10.1021/jo100383u.
The striped cucumber beetle, Acalymma vittatum, is a cause of major damage to cucurbit crops in North America. To develop an environmentally benign plant protection strategy, recent research has focused on identifying sex pheromones of the cucumber beetle. In this context, we developed the asymmetric total synthesis of the aggregation pheromone of A. vittatum, Vittatalactone, to determine its absolute configuration and to further examine the pheromone response in field studies. The synthesis features an enzyme-catalyzed approach toward the deoxypropionate structural motif. A preformed organocopper reagent could then be coupled in an enantioselective o-DPPB-directed allylic substitution with a functionalized o-DPPB-ester. By means of this efficient transformation, Vittatalactone could be obtained following a highly convergent synthetic process.
横纹龟形瓢虫（Acalymma vittatum）是北美的一种主要瓜类作物害虫。为了制定一种环境友好的植物保护策略，最近的研究集中在鉴定黄瓜甲虫的性信息素上。在这种情况下，我们开发了 A. vittatum 聚集信息素 Vittatalactone 的不对称全合成，以确定其绝对构型，并在田间研究中进一步研究信息素反应。该合成的特点是采用酶催化方法构建去氧丙酸盐结构基序。然后，预形成的有机铜试剂可以在对映选择性的 o-DPPB 导向烯丙基取代反应中与功能化的 o-DPPB-酯偶联。通过这种高效的转化，可以在高度收敛的合成过程中得到 Vittatalactone。
