Computational advances aiding mechanistic understanding of silver-catalyzed carbene/nitrene/silylene transfer reactions.

Graphical abstract Theoretical advances on the mechanistic study of Ag-catalyzed carbene/nitrene/silylene transfer reactions were summarized in this review, which could be considered to involve two major steps: Ag–carbene/nitrene/silylene complex formation and the subsequent transformation of these complexes. Highlights • DFT studies on the mechanism of Ag-catalyzed group transfer reactions are summarized. • The mechanism consists of Ag–carbene/nitrene/silylene formation and transformation. • The mechanism is related to the electronic behaviors of Ag–carbene/nitrene/silylene. Abstract Carbene and its isoelectronic species nitrene and silylene, have long been considered reactive intermediates in organic synthesis. Ag-catalyzed carbene/nitrene/silylene transfer reactions have emerged as an important topic because they have made remarkable progress in organic synthesis. A series of theoretical investigations on the mechanism of these reactions is important to ensure their thorough understanding and aid design of new synthetic methodologies. Here, a mechanistic overview of Ag-catalyzed carbene/nitrene/silylene transfer reactions is given, which can be separated into two major steps including Ag–carbene/nitrene/silylene complex formation and the subsequent transformation of these complexes. Theoretical studies revealed that Ag–carbene and Ag–silylene complexes can be considered as typical Fischer-type complexes, in which the carbene/silylene moiety behaves as both a sp σ donor and p π acceptor. Conversely, the triplet Ag–nitrene complexes are usually more stable than the singlet ones because of the higher electronegativity of nitrogen than those of carbon and silicon. Density functional theory calculations have indicated that the triplet state of an Ag–nitrene complex has two unpaired electrons that are mainly localized on nitrogen. In this review, theoretical studies on the generation of Ag–carbene/nitrene/silylene complexes are systematically summarized. Moreover, the nucleophilic functionalization of Ag–carbene/nitrene/silylene complexes with halogen, hydroxyl, carbonyl, alkane, or arene groups are also considered theoretically. We believe that the mechanistic details discussed here will be of great importance for rational design of desired catalytic cycles and reactions. [ABSTRACT FROM AUTHOR]