Department of Chemistry, Wroclaw University of Environmental and Life Sciences, 50-375 Wrocław, Poland.
Department of Invertebrate Zoology, Nicolaus Copernicus University, 87-100 Toruń, Poland.
Molecules. 2018 Jun 23;23(7):1516. doi: 10.3390/molecules23071516.
Hydrolysis of (±)-β-aryl-γ-ethylidene-γ-lactones by fungal strain AM370 afforded (−)-()-γ-ethylidene-γ-lactones ⁻ and (+)-()-γ-ketoacids ⁻. Enantiomeric purity of the unreacted lactones was strictly related to a size of an aryl substituent at C-4 of γ-lactone ring, with the highest (77%) obtained for the (−)-()-γ-ethylidene-γ-lactone possessing unsubstituted benzene ring () and the lowest one (15%) determined for the (−)-()-γ-ethylidene-γ-lactone with bulky 1,3-benzodioxole system (). Lactones ⁻, both racemic and enantiomerically enriched, as well as products of their hydrolysis showed varying degrees of feeding deterrent activity against lesser mealworm, Panzer, which depended on the structure of the compound and the developmental stage of the lesser mealworm. In the case of adults, more active were γ-lactones ⁻, compared with ketoacids ⁻. Only in the case of lactone was the effect of configuration of stereogenic center on the activity found. Particularly strong deterrents against this stage (T > 180) were racemic and (−)-()-γ-ethylidene-γ-lactone with -methoxysubstituted phenyl ring ().
（±）-β-芳基-γ-亚乙基-γ-内酰胺经真菌菌株 AM370 水解得到（-）-（）-γ-亚乙基-γ-内酰胺 ⁻ 和（+）-（）-γ-酮酸 ⁻ 。未反应的内酰胺的对映体纯度与 γ-内酰胺环 C-4 上芳基取代基的大小严格相关，其中未取代苯环（）的（-）-（）-γ-亚乙基-γ-内酰胺获得的对映体纯度最高（77%），而带有大体积 1,3-苯并二恶唑系统（）的（-）-（）-γ-亚乙基-γ-内酰胺的对映体纯度最低（15%）。 ⁻ 内酰胺，无论是外消旋体还是对映体富集体，以及它们水解的产物，都对小菜蛾 Panzer 表现出不同程度的摄食抑制活性，这取决于化合物的结构和小菜蛾的发育阶段。对于成虫，γ-内酰胺 ⁻ 比酮酸 ⁻ 更具活性。只有在内酯的情况下，才发现手性中心的构型对活性有影响。对该阶段（T > 180）具有特别强抑制作用的是外消旋体和（-）-（）-γ-亚乙基-γ-内酰胺，其苯环带有甲氧基取代基（）。
