Enantioselective Synthesis of Chiral-at-Cage o-Carboranes via Pd-Catalyzed Asymmetric B-H Substitution
Enantioselective Synthesis of Chiral-at-Cage o-Carboranes via Pd-Catalyzed Asymmetric B-H Substitution
复制标题
通过 Pd 催化不对称 B-H 取代对映选择性合成手性笼邻碳硼烷
DOI：
10.1021/jacs.8b01754
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发表时间：
2018-04-04
影响因子：
15
通讯作者：
Xie, Zuowei
中科院分区：
文献类型：
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作者：
Cheng, Ruofei;Li, Bowen;Xie, Zuowei
由于二十面体碳硼烷在医药和材料化学中有着广泛的应用，碳硼烷笼型手性是人们非常感兴趣的一个突出问题。具有光学活性的碳硼衍生物的手性与多面体上的取代模式有关，它的合成将为碳硼烷化学开辟新的途径。我们报道了一种通过钯催化的不对称分子内B-H芳基化和环化策略来实现具有高区域和对映体选择性的邻碳硼烷的手性笼式芳基化反应的有效方法。这是碳硼烷对映体选择性反应的第一个例子，为构建具有新骨架的手性笼状化合物提供了一种有效的方法。
Carborane cage chirality is an outstanding issue of great interest as the icosahedral carboranes have wide applications in medicinal and materials chemistry. The synthesis of optically active carborane derivatives, whose chirality is associated with the substitution patterns on the polyhedron, will open new avenues to carborane chemistry. We report herein an efficient method to achieve chiral-at-cage arylation of o-carboranes with high regio- and enantioselectivities by a strategy of palladium-catalyzed asymmetric intramolecular B-H arylation and cyclization. This represents the first example of the enantioselective reaction on carboranes, providing an efficient way for the construction of chiral-at-cage compounds with new skeletons.