Abstract
The reaction mechanism of Cu-catalyzed C-H hydroxylation/C-S coupling was studied using electrospray ionization high resolution mass spectrometry (ESI-HR MS) and density functional theory calculations (DFT). Notably, a series of CuI and CuIII complexes were observed as key intermediates and identified using ESI-HR MS. Furthermore, a catalyst cycle involving proton abstraction/oxidative addition/reductive elimination was proposed. This study is important and valuable with respect to C-H functionalization.
Highlights
C-H bond activation is a hot topic in modern organic chemistry [1,2,3]
Based on ESI-HR MS experiments and density functional theory calculations (DFT) calculations, we propose a proton abstraction/oxidative addition/reductive elimination reaction mechanism of Cu-catalyzed C-H hydroxylation/C-S coupling
The reaction of vinyl halides with thiophenol was chosen as the model reaction (Scheme 1, n = 1)
Summary
C-H bond activation is a hot topic in modern organic chemistry [1,2,3]. There are many methods to activate the C-H bonds of molecules, C-H activation in pure hydrocarbons is still a challenge [4,5,6]. Most methods involve transition-metal catalysis, where a continuum of reaction mechanisms exists. Some C-H activation reactions have been shown to proceed much more efficiently and selectively through ligand direction [7,8,9]. Such assistance is well known for metal catalysts with ligands [10]. The investigation of C-H bond activation mechanisms can provide information on key reaction factors, allowing for the design of new reactions [12,13,14]. C-H bond activation mechanisms are difficult to study due to the complex interactions between the reaction parameters [15,16]. Mechanistic studies proposed an electrophilic aromatic substitution mechanism [17,18,19], for which large primary kinetic isotope effects were observed [20]
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