Enantioselective Hydrophosphination of Terminal Alkenyl Aza‐Heteroarenes

This paper presents a Mn(I)‐catalysed methodology for the enantioselective hydrophosphination of terminal alkenyl aza‐heteroarenes. The catalyst operates through H−P bond activation, enabling successful hydrophosphination of a diverse range of alkenyl‐heteroarenes with high enantioselectivity. The presented protocol addresses the inherently low reactivity and the commonly encountered suboptimal enantioselectivities of these challenging substrates. As an important application we show that this method facilitates the synthesis of a non‐symmetric tridentate P,N,P‐containing ligand like structure in just two synthetic steps using a single catalytic system. Stereoselective hydrophosphination of alkenes is a promising route to chiral phosphorus compounds, but the use of alkenyl‐heteroarenes is challenged by their low reactivity and control of stereoselectivity. Here we present a general Mn(I)‐catalysed enantioselective hydrophosphination of alkenyl aza‐heteroarenes. The method was applied to a wide range of alkenyl heterocycles and provided access to a non‐symmetric P,N,P ligand structure.