期刊
ORGANOMETALLICS
卷 33, 期 19, 页码 5525-5534出版社
AMER CHEMICAL SOC
DOI: 10.1021/om5007903
关键词
-
资金
- Australian Research Council
- U.S. National Institutes of Health [GM 073836]
A combination of experimental and density functional theory (DFT) investigations suggests that the Cu-catalyzed fluorination of unsymmetrical diaryliodonium salts with general structure [Mes(Ar)I](+) in N,N'-dimethylformamide proceeds through a CuI/CuIII catalytic cycle. A low concentration of fluoride relative to combined iodonium reagent plus copper ensures that [Mes(Ar)I](+) is available as the reactive species for oxidative Ar+ transfer to a CuI center containing one or two fluoride ligands. A series of different possible CuI active catalysts (containing fluoride, triflate, and DMF ligands) have been evaluated computationally, and all show low-energy pathways to fluorinated products. The oxidation of these CuI species by [Mes(Ar)I](+) to form cis-Ar(F)Cu-III intermediates is proposed to be rate-limiting in all cases. Ar-F bond-forming reductive elimination from CuIII is computed to be very facile in all of the systems examined. The conclusions of the DFT experiments are supported by several experimental studies, including tests showing that CuI is formed rapidly under the reaction conditions and that the fluoride concentration strongly impacts the reaction yields/selectivities.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据