Conformer-related pathways in cycloaddition of vinylaziridines and alkynes catalyzed by rhodium(I)-complex

作者：Chen, Jian; Huang, Minmin; Xi, Fei^*

来源：Chemical Physics Letters, 2018, 713: 21-25.

DOI：10.1016/j.cplett.2018.10.011

• EFFECTIVE CORE POTENTIALS
• VINYL AZIRIDINES
• INTERMOLECULAR CYCLOADDITIONS
• ENE-VINYLCYCLOPROPANES
• MOLECULAR CALCULATIONS
• DENSITY FUNCTIONALS
• BOND INSERTION
• ORIGINS
• METAL
• MECHANISM

The conformer-related reaction pathways in the cycloaddition of vinylaziridines with alkynes were calculated using DFT methods. The calculated results reveal that the ring-opening products of vinylaziridines possess two different conformers with the specific sites available for coordination of alkynes. The formed alkyne-coordinated complexes results in the different C-N bond addition intermediates. In the cycloaddition reaction catalyzed by [Rh(eta(6) -C10H8)(COD)]SbF6, the intermediate needs an isomerization to yield the final [5 + 2] cycloaddition product. In the reaction catalyzed by [Rh(NBD)(2)]BF4, such an isomerization is dispensable to yield the final [3 + 2] cycloaddition product.

• 出版日期2018-12
• 单位华东师范大学