金属有机化学ppt.pptxVIP

Rhodium(III)-Catalyzed Amidation of Unactivated C(sp3)-H BondsHe Wang, Guodong Tang, and Xingwei Li* 主讲人：曾晚婷 C-H Activation Research background 2 The significance of C(sp3)-H activation leading to C-N bond formation has been extensively exemplified because C-N linkages are ubiquitous in pharmaceuticals, biologically active compounds, and natural products. Consequently, the direct amination/amidation of unactivated C(sp3)-H bonds has received increasing attention. In the past decade, only limited examples of direct amination of C(sp3)-H Bonds has been reported by using palladium, rhodium(II),copper, iridium,and other catalysts. Recently, rhodium(III)-catalyzed C-H activation has been increasingly explored, and provides unique synthetic methodologies with high activity,selectivity, broad substrate scope, and functional-group tolerance. Despite these attractive processes, the coupling reactions are mostly based on C(sp2)-H activation. 3 Research background Thus,there are only a few examples on the functionalization of unactivated C(sp3)-H bonds using rhodium(III) catalysis, as in the coupling with alkynes, activated forms of arenes,and azides. Recently, Chang and co-workers reported an elegant iridium(III)-catalyzed amidation for a broad scope of C(sp3)-H bonds using organic azides. Despite the progress, rhodium(III)-catalyzed C(sp3)-H activation reactions, especially amidation reactions, typically suffer from limited substrate scope and harsh reaction conditions, and only amidation of benzylic C-H bonds, such as that in 8-methylquinolines, has been realized. 4 The challenges associated with C(sp3)-H bond activation can be ascribed to the steric hindrance of C(sp3)-H bonds and the low reactivity of the resulting Rh-C(alkyl) species. Therefore, the stability, coordinating capacity, and reactivity of the coupling partner are major criteria for our design. Research background 5 We now report a mild rhodium(III)-catalyzed C(sp3)-H amidation for a broad scope of