Agnideep Das, Brendan Twamley, Oscar R. Kelly, Chakadola Panda, Paul Richardson, Aidan R. McDonald
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引用次数: 0
Abstract
The heme paradigm where Fe=O acts as the C−H oxidant and Fe−OH rebounds with the formed carbon-centered radical guides the design of the prototypical synthetic hydroxylation catalyst. We are exploring methods to evolve beyond the metal-oxo oxidant and hydroxide rebound, to incorporate a wider array of functional group. We have demonstrated the application of CoII(OTf)2 (10 mol% catalyst; OTf=trimfluoromethanesulfonate) in combination with polydentate N-donor ligands (e. g. BPMEN=N,N′-dimethyl-N,N′-bis(pyrid-2-ylmethyl)ethane-1,2-diamine) and Selectfluor in the oxidative fluorination of saturated hydrocarbons in high yields. The addition of CsF to the reaction mixture induced near-quantitative yields of fluorinated saturated hydrocarbons (>90 % yield of fluorinated product). For 1-hydroxy, 1-acetyl, 1-carboxy-, and 1-acetamido-adamantane, we demonstrated selective fluorination at the 3-position. We propose two mechanisms for the CoII-catalyzed reaction: either (i) an N-radical, derived from Selectfluor, acted as the C−H oxidant followed by radical rebound with CoIII−F; or (ii) a CoIV−(F)2 species was the C−H oxidant followed by radical rebound with CoIII−F. Our combined spectroscopic, kinetic, and chemical trapping evidence suggested that an N-radical was not the active oxidant. We concluded that a CoIV−(F)2 species was the likely active oxidant and CoIII−F was the likely F-atom donor to a carbon centered radical producing a C−F bond.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.