Non-Noble-Metal Metal-Organic-Framework-Catalyzed Carboxylative Cyclization of Propargylic Amines with Atmospheric Carbon Dioxide under Ambient Conditions.

The coupling reaction of propargylic amines and carbon dioxide (CO2) to synthesize 2-oxazolidinones is an important reaction in industrial production, and yet harsh reaction conditions and noble-metal catalysts are often required to achieve high product yields. Herein, one novel noble-metal-free three-dimensional framework, [Mg3Cu2I2(IN)4(HCOO)2(DEF)4]n (1), assembled by magnesium and copper clusters was synthesized and applied to this reaction. Compound 1 displays excellent solvent stability. Importantly, 1, acting as heterogeneous catalyst, can highly catalyze the cyclization of propargylic amines with CO2 under atmospheric pressure at room temperature, which can be recycled at least five times without an obvious decrease of the catalytic activity. NMR spectroscopy, coupled with 13C-isotope- and deuterium-labeling experiments, clearly clarifies the mechanism of this catalytic system: CO2 was successfully captured and converted to the product of 2-oxazolidinones, the C≡C bond of propargylic amines can be effectively activated by 1, and proton transfer was involved in the reaction process. Density functional theory calculations are further conducted to uncover the reaction path and the crucial role of compound 1 during the reaction.