Modular functionalization of allenes to aminated stereotriads.
Modular functionalization of allenes to aminated stereotriads.
复制标题
DOI：
10.1021/ja304859w
复制
发表时间：
2012-07-04
影响因子：
15
通讯作者：
Schomaker JM
中科院分区：
文献类型：
--
作者：
Adams CS;Boralsky LA;Guzei IA;Schomaker JM
含氮的立体三元化合物--含有三个相邻的立体定义碳的化合物--通常存在于重要的生物分子中。然而，含有这些基序的分子的制备可能是具有挑战性的。在这里，我们描述了一种模块氧化方案，它将取代的丙二烯转化为形式为C-X/C-N/CY的三官能化胺。关键步骤采用了Rh催化的联烯分子内转化为应变双环亚甲基氮杂环丙烷。这种反应性中间体进一步细化为目标产物，通常在一个反应容器中，并有效地将联烯的轴手性转移到立体三元中的点手性。
Nitrogen-containing stereotriads- compounds with three adjacent stereodefined carbons- are commonly found in biologically important molecules. However, the preparation of molecules bearing these motifs can be challenging. Herein, we describe a modular oxidation protocol which converts a substituted allene to a triply functionalized amine of the form C-X/C-N/CY. The key step employs a Rh-catalyzed intramolecular conversion of the allene to a strained bicyclic methylene aziridine. This reactive intermediate is further elaborated to the target products, often in one reaction vessel and with effective transfer of the axial chirality of the allene to point chirality in the stereotriad.