The background and recent breakthroughs in the single-electron-transfer (SET) reactions with trivalent tertiary phosphines are summarized and discussed in detail, and an outlook in the developments within this field is provided.

The last couple of decades have witnessed tremendous development within N-heterocyclic carbene (NHC) organocatalysis. NHCs have been used as powerful organic catalysts in asymmetric synthesis. Although great achievements have been made in asymmetric NHC catalysis, their applications in kinetic resolution (KR), dynamic kinetic resolution (DKR), and desymmetrization processes have been relatively less developed. Moreover, limited activation modes have been involved in these processes. This review provides an overview of the NHC-organocatalyzed KR, DKR, and desymmetrization reactions in the preparation of chiral functional molecules. The aim is to highlight both the importance and elegance of these methods in the construction of challenging chiral compounds and to provide our own perspective on future development in this direction.