Mechanistic, crystallographic, and computational studies on the catalytic, enantioselective sulfenofunctionalization of alkenes.
Mechanistic, crystallographic, and computational studies on the catalytic, enantioselective sulfenofunctionalization of alkenes.
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DOI：
10.1038/nchem.2109
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发表时间：
2014-12
期刊：
影响因子：
21.8
通讯作者：
Wang H
中科院分区：
文献类型：
--
作者：
Denmark SE;Hartmann E;Kornfilt DJ;Wang H
将邻位杂原子取代基立体控制地引入有机分子中是增加价值和功能的最有效方法之一。尽管存在许多引入含氧和氮取代基的方法，但相比之下，用于引入含硫取代基的立体控制方法的数量就显得相形见绌了。这些实验室之前的报告描述了烯烃的硫基官能化，其构建了邻位碳-硫和碳-氧、碳-氮以及具有高水平的非对映专一性和对映选择性的碳-碳键。该过程是通过路易斯酸的路易斯碱活化的概念实现的，该概念提供了第 16 族亲电子试剂的活化。为了为扩大底物范围和提高选择性奠定基础，我们对催化活性物质进行了全面的研究。从动力学、晶体学和计算方法中收集到的见解导致引入了新的磺化剂家族，其选择性显着增强。
The stereocontrolled introduction of vicinal heteroatomic substituents into organic molecules is one of the most powerful ways of adding value and function. Whereas many methods exist for the introduction of oxygen- and nitrogen-containing substituents, the number stereocontrolled methods for the introduction of sulfur-containing substituents pales by comparison. Previous reports from these laboratories have described the sulfenofunctionalization of alkenes that construct vicinal carbon-sulfur and carbon-oxygen, carbon-nitrogen as well as carbon-carbon bonds with high levels of diastereospecificity and enantioselectivity. This process is enabled by the concept of Lewis base activation of Lewis acids that provides activation of Group 16 electrophiles. To provide a foundation for expansion of substrate scope and improved selectivities, we have undertaken a comprehensive study of the catalytically active species. Insights gleaned from kinetic, crystallographic and computational methods have led to the introduction of a new family of sulfenylating agents that provide significantly enhanced selectivities.