Asymmetric catalysis with readily available, cheap, and non-toxic alkaline earth metal catalysts represents a sustainable alternative to conventional synthesis methodologies. In this context, we describe the development of a first Mg -catalyzed enantioselective hydroboration providing the products with excellent yields and enantioselectivities. NMR spectroscopy studies and DFT calculations provide insights into the reaction mechanism and the origin of the enantioselectivity which can be explained by a metal-ligand cooperative catalysis pathway involving a non-innocent ligand.
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