Catalytic construction of non-carbon stereocenters by N-heterocyclic carbenes

Chirality is widely present in natural products, pharmaceutical compounds, and functional molecules. N-heterocyclic carbene (NHC) catalysis has emerged as a pivotal strategy for constructing stereocenters, leveraging its strong σ-donating capability and tunable steric and electronic environment. Although catalytic asymmetric synthesis of carbon stereocenters has achieved significant maturity, the construction of non-carbon stereocenters continues to face persistent challenges. Long-standing limitations, including configurational inversion induced by lone electron pairs, poor dynamic stability, and limited generality of catalytic systems, have substantially hindered progress in this domain. In recent years, NHC catalysis has garnered extensive attention for its significant advances in the construction of non-carbon chiral stereocenters, including silicon, sulfur, phosphorus, nitrogen, and boron atoms. This review systematically summarizes the latest progress and application potential of NHC catalysis in this field, aiming to provide a theoretical foundation and methodological guidance for future research.