Xu Chunping, Schwartz Chris, Raible Joseph, Dussault Patrick H
Department of Chemistry, University of Nebraska-Lincoln, Lincoln, Nebraska, 68588-0304.
Tetrahedron. 2009 Nov 21;65(47):9680-9685. doi: 10.1016/j.tet.2009.09.068.
The stereospecific intramolecular alkylation of a hydroperoxyacetal provides the basis for the first asymmetric synthesis of the dioxane propionate core of the peroxyplakorates. Chemoselective hydrometallation of an alkyne in the presence of a peroxide is used to introduce a synthon for the polyunsaturated side chains of the peroxyplakorates. The route suggests a general solution for the 1,2-dioxane unit in many peroxide natural products.
氢过氧缩醛的立体专一性分子内烷基化反应为过氧普拉卡酯的二氧杂环己烷丙酸酯核心的首次不对称合成提供了基础。在过氧化物存在下，炔烃的化学选择性氢金属化反应被用于引入过氧普拉卡酯多不饱和侧链的合成子。该路线为许多过氧化物天然产物中的1,2 - 二氧杂环己烷单元提供了一种通用的合成方法。
