Pd(OAc)_(2) is an extensively utilized palladium source in the palladium initiated transformations either directly or as a catalyst precursor. However, the comprehension of the real structure of Pd(OAc)_(2) in solutio...Pd(OAc)_(2) is an extensively utilized palladium source in the palladium initiated transformations either directly or as a catalyst precursor. However, the comprehension of the real structure of Pd(OAc)_(2) in solution is still vague. In this work, the structure of palladium acetate in solution was studied in detail by using X-ray absorption fine structure (XAFS) spectroscopy. The results demonstrate that monomer is the main form for Pd(OAc)_(2) in the solution of 1,4-dioxane, N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF), 1,2-dimethoxyethane (DME), MeCN and dimethyl sulfoxide (DMSO). In addition, Pd(II) could be reduced to Pd(0) in ethanol solution. The structural information in this research will benefit the understanding of the mechanism of Pd(OAc)_(2) involved organic reactions.展开更多
Selective C–H bond functionalization has been emerged as a versatile strategy for the construction of new chemical bonds. In the past decades, the directing group(DG)-assisted C–H bond activation has been developed ...Selective C–H bond functionalization has been emerged as a versatile strategy for the construction of new chemical bonds. In the past decades, the directing group(DG)-assisted C–H bond activation has been developed as one of the most efficient methods for selective C–H functionalization. Although a great progress has been made by utilizing this traditional method, developing new strategy for selective C–H bond functionalization is still highly demanded. Hence, a novel oxidation-induced C–H bond functionalization method was demonstrated in this work. By this new method, ortho-C(sp2)–H chlorination of N-substituted 2-naphthylamine was realized in a highly selective manner.展开更多
基金This work was supported by the National Natural Science Foundation of China(No.21520102003)the Hubei Province Natural Science Foundation of China(No.2017CFA010)The Program of Introducing Talents of Discipline to Universities of China(111 Program)is also appreciated.All the XAFS data were collect-ed at beam line 44A of the TPS.
文摘Pd(OAc)_(2) is an extensively utilized palladium source in the palladium initiated transformations either directly or as a catalyst precursor. However, the comprehension of the real structure of Pd(OAc)_(2) in solution is still vague. In this work, the structure of palladium acetate in solution was studied in detail by using X-ray absorption fine structure (XAFS) spectroscopy. The results demonstrate that monomer is the main form for Pd(OAc)_(2) in the solution of 1,4-dioxane, N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF), 1,2-dimethoxyethane (DME), MeCN and dimethyl sulfoxide (DMSO). In addition, Pd(II) could be reduced to Pd(0) in ethanol solution. The structural information in this research will benefit the understanding of the mechanism of Pd(OAc)_(2) involved organic reactions.
基金supported by the National Natural Science Foundation of China (21390402, 21520102003, 21702150)the National Basic Research Program of China (2012CB725302)+1 种基金the CAS Interdisciplinary Innovation Team and the Hubei Province Natural Science Foundation of China (2017CFA010)China Postdoctoral Science Foundation (BX201600114, 2016M602340)
文摘Selective C–H bond functionalization has been emerged as a versatile strategy for the construction of new chemical bonds. In the past decades, the directing group(DG)-assisted C–H bond activation has been developed as one of the most efficient methods for selective C–H functionalization. Although a great progress has been made by utilizing this traditional method, developing new strategy for selective C–H bond functionalization is still highly demanded. Hence, a novel oxidation-induced C–H bond functionalization method was demonstrated in this work. By this new method, ortho-C(sp2)–H chlorination of N-substituted 2-naphthylamine was realized in a highly selective manner.
