Abstract
A computational mechanistic study of gold-catalyzed intermolecular alkene difunctionalization/cross-coupling of aryl iodides with methanol was studied. By calculating the corresponding initial oxidative addition step mediated by the related chelating (P,N) ligands, our results uncover the essential roles of hemilabile Me-Dalphos to promote the oxidative addition process by minimizing the distortion of substrate and catalyst. For the nucleophile methanol, by comparing the mechanism of intermolecular alkene difunctionalization versus cross-coupling, the C(sp2)–C(sp3) reductive elimination is found more favorable than the corresponding C(sp2)–O formation, which contributes to the exclusive intermolecular alkene oxyarylation product. Furthermore, the different reactivity and selectivity of other nucleophiles such as tosyl amine and 1,3,5-trimethoxybenzene were compared. This mechanistic understanding will provide valuable guidance for the further development and wider application of gold-catalyzed redox reactions in synthetic chemistry.
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