The metal-catalyzed asymmetric addition of phosphorus nucleophiles is one of the most efficient and reliable approaches for the construction of new carbon–phosphorus bonds. In recent years, great achievements have been made in this area, and many powerful methods have been developed for these transformations with high efficiency, low ligand loading and excellent selectivity. This tutorial review covers recent efforts in the constructions of P–C bonds through asymmetric additions of phosphorus nucleophiles including dialkyl phosphites, secondary phosphine oxides and secondary phosphines.

Chirality plays a fundamental role in biology and chemistry and the precise control of chirality in a catalytic conversion is a key to modern synthesis most prominently seen in the production of pharmaceuticals. In enantioselective metal-based catalysis, access to each product enantiomer is commonly achieved through ligand design with chiral bisphosphines being widely applied as privileged ligands. Switchable phosphine ligands, in which chirality is modulated through an external trigger signal, might offer attractive possibilities to change enantioselectivity in a catalytic process in a non-invasive manner avoiding renewed ligand synthesis. Here we demonstrate that a photoswitchable chiral bisphosphine based on a unidirectional light-driven molecular motor, can be used to invert the stereoselectivity of a palladium-catalysed asymmetric transformation. It is shown that light-induced changes in geometry and helicity of the switchable ligand enable excellent selectivity towards the racemic or individual enantiomers of the product in a Pd-catalysed desymmetrization reaction.