A useful and convenient method for sp3 C–P­(O) bond formation via direct regioselective hydrophosphinylation of simple and readily available alkenes using a lanthanum-based N,N-dimethylbenzylamine complex (La­(DMBA)3) as a precatalyst is demonstrated. The reaction proceeds with perfect atom economy for a wide range of styrenes with secondary phosphine oxides, giving moderate to excellent yields.

An intermolecular sulfenoamination reaction utilizing a stable sulfur precursor with a broad range of alkene structures is described. More importantly, these reactions proceed in a highly regio- and stereoselective manner to afford interesting heterocyclic motifs ready for biological studies. In addition, a highly regiodivergent approach to access the opposite regioisomers for styrene derivatives was also developed.

We report an attractive and efficient synthetic approach to form Si–N bonds via the heterodehydrocoupling of silanes and amines catalyzed by a lanthanum-based N,N-dimethylbenzylamine complex [La(DMBA)3]. A wide variety of primary and secondary amines were well-suited coupling partners with primary, secondary, and tertiary silanes for this catalytic transformation, resulting in the formation of numerous silylamines in high efficiency and moderate-to-excellent yields under mild conditions.

A high-yielding and atom-efficient protocol for the double hydrophosphorylation of nitriles using a lanthanum-based N,N-dimethylbenzylamine complex (La­(DMBA)3) as a precatalyst is reported. This method provides a straightforward and convenient approach for the synthesis of biologically important organophosphorus compounds known as N-(α-phosphoryl)­amidophosphates in good to excellent yields. Nitriles with a broad range of additional functionality were tolerated, including those with halides, ethers, amines, and pyridyl groups.