How Dirhodium Catalyst Controls the Enantioselectivity of [3 + 2]-Cycloaddition between Nitrone and Vinyldiazoacetate: A Density Functional Theory Study
详细信息 查看全文
- 作者：Xin Yang ; Yongsheng Yang ; Robert J. Rees ; Qi Yang ; Zhiyue Tian ; Ying Xue
- 刊名：Journal of Organic Chemistry
- 出版年：2016
- 出版时间：September 2, 2016
- 年：2016
- 卷：81
- 期：17
- 页码：8082-8086
- 全文大小：450K
- 年卷期：0
- ISSN：1520-6904
文摘
The origin of enantioselectivity in the dirhodium-catalyzed [3 + 2]-cycloaddition of nitrone and vinyldiazoacetate has been investigated using dispersion-corrected density functional theory. Taking a more realistic account of bulky ligands in models of the dirhodium catalyst when investigating its catalytic behavior is crucial for describing the effects resulting from a high level of asymmetric induction. More than one active site can be located and the extra reactivity is provided by an electron-donation interaction between the substrate and an additional Rh2L4 catalyst.