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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. [ABSTRACT FROM AUTHOR]

The asymmetric reduction of 1,2‐diketones for the synthesis of optically active 1,2‐diols, especially 1,2‐anti‐diols, remains a formidable challenge. In this paper, we describe the first highly stereoselective hydrosilylation of unsymmetrical vicinal diketones with PhSiH3 by using a chiral frustrated Lewis pair (FLP) catalyst, giving a variety of 1,2‐diaryl‐1,2‐anti‐diols in high yields with excellent d.r. values and up to 97 % ee. The chiral FLP catalyst exhibits the ability to control regio‐, diastereo‐ and enantioselectivites concurrently. [ABSTRACT FROM AUTHOR]