Asymmetric Synthesis with Silicon‐Based Bulky Amino Organocatalysts

Recent years have witnessed an explosive growth in the field of amino organocatalysis, especially in asymmetric enamine and iminium catalysis. Except for the obvious interaction between organocatalyst and substrate, the impact of bulky side group ons stereoselectivity is not as simple as one could imagine. Within the development of bulky site‐stereoselective organocatalysts, functional silyl organocatalysts with a bulky silicon group are promising and meet the high standards of modern synthetic methods. This review focuses on the recent advances in the synthetic applications of silicon‐based, bulky amino organocatalysts in which catalysts containing an organosilicon moiety or group play a formative role in controlling both the course of the reaction as well as the stereoselectivity.