Kim Ye Ji, Kim Sun Min, Cho Eun Jin, Hosono Hideo, Yang Jung Woon, Kim Sung Wng
Department of Energy Science , Sungkyunkwan University , Suwon 440-746 , Korea . Email:
Center for Integrated Nanostructure Physics , Institute for Basic Science , Sungkyunkwan University , Suwon 440-746 , Korea.
Chem Sci. 2015 Jun 1;6(6):3577-3581. doi: 10.1039/c5sc00933b. Epub 2015 Apr 13.
A simple and highly efficient transfer hydrogenation of alkynes and alkenes by using a two-dimensional electride, dicalcium nitride ([CaN]·e), as an electron transfer agent is disclosed. Excellent yields in the transformation are attributed to the remarkable electron transfer efficiency in the electride-mediated reactions. It is clarified that an effective discharge of electrons from the [CaN]·e electride in alcoholic solvents is achieved by the decomposition of the electride alcoholysis and the generation of ammonia and Ca(OPr). We found that the choice of solvent was crucial for enhancing the electron transfer efficiency, and a maximum efficiency of 80% was achieved by using a DMF mixed isopropanol co-solvent system. This is the highest value reported to date among single electron transfer agents in the reduction of C-C multiple bonds. The observed reactivity and efficiency establish that electrides with a high density of anionic electrons can readily participate in the reduction of organic functional groups.
公开了一种使用二维电子化物氮化二钙（[CaN]·e）作为电子转移剂对炔烃和烯烃进行简单且高效的转移氢化反应。该转化反应中的优异产率归因于电子化物介导反应中显著的电子转移效率。据阐明，通过电子化物的分解（醇解）以及氨和Ca(OPr)的生成，可在醇类溶剂中实现[CaN]·e电子化物的有效电子释放。我们发现，溶剂的选择对于提高电子转移效率至关重要，使用DMF与异丙醇的混合共溶剂体系可实现高达80%的最大效率。这是迄今为止在碳 - 碳多重键还原中单一电子转移剂所报道的最高值。观察到的反应活性和效率表明，具有高密度阴离子电子的电子化物能够轻易参与有机官能团的还原反应。
