Synthesis, Characterization and Catalytic Applications of N-Heterocyclic Carbene Silver(I) Complexes.

• Main Authors: Lin, Hsi-Yin, 林羲尹
• Other Authors: Yu, Shu-Chun
• Format: Others
• Language: zh-TW
• Published: 2015
• Online Access: http://ndltd.ncl.edu.tw/handle/ht63hd

碩士 === 國立中正大學 === 化學暨生物化學研究所 === 103 === Silver was used by human for thounds of year. It is a low toxic and earth abundant metal. Furthermore, silver is much cheaper than most of noble metals and can be recycled easily. Therefore, silver-catalyzed organic reactions have attracted attention recently. In this present study, we successfully synthesized three silver(I) N-heterocyclic carbene complexes (NHCs), [Ag(hmim)2][PF6] (9), [Ag(2-MePybim)][PF6] (10), and [Ag(Mesbim)CH3CN][PF6] (11), by direct reaction of Ag2O and imidazolium salts, (Hmim)HPF6 (2), (2-MePybim)HPF6 (5), and (Mesbim)HPF6 (8). And all 9, 10 and 11 were characterized by 1H NMR, 13C NMR, ESI-mass, FT-IR, AA and EA spectroscopies. Muliticomponent reactions (MCRs) have been established as a extremely important processes in organic synthesis. And the aldehydes, alkynes, and amine coupling (A3 coupling) is one of them, which gives coupling products, propargylamines, as major skelentins for the preparations of many biologically active natural materials. A series of A3 coupling reaction of aldehydes, pyrrolidine, and phenylacetylene were catalyzed by 9, 10 and 11 with a catalyst loading of 4 mol% at 100 oC to gives high conversion in 30 minutes. Furthermore, we also demonstrated that the coupling reaction can be further accelerated under microwave flash heating conditions. By this, we first studied that conversion and yield are not consistent in A3 coupling in more detail. In addition, a series of hydroamination reaction of amine and ethyl propiolate with a catalyst loading of 4 mol% of 9, 10 and 11 were also carried out at 60 oC to give corresponding products with high yiled in 4 hours. And can be further accelerated under microwave flash heating conditions in the same way.