Asymmetric Magnesium-Catalyzed Hydroboration by Metal-Ligand Cooperative Catalysis.

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.

Magnesium-Catalyzed Hydroboration of Terminal and Internal Alkynes.

A magnesium-catalyzed hydroboration of alkynes providing good yields and selectivities for a wide range of terminal and symmetrical and unsymmetrical internal alkynes has been developed. The compatibility with many functional groups makes this magnesium catalyzed procedure attractive for late stage functionalization. Experimental mechanistic investigations and DFT calculations reveal insights into the reaction mechanism of the magnesium catalyzed protocol.