The Diarylprolinol Silyl Ethers: Ten Years After

Asymmetric organocatalysis has experienced an incredible development since the beginning of this century. The expansion of the field has led to a large number of efficient types of catalysts. One group, the diarylprolinol silyl ethers, was introduced in 2005 and has been established as one of the most frequently used in aminocatalysis. In this Minireview, we will take a look in the rear‐view mirror, ten years after the introduction of the diarylprolinol silyl ethers. We will focus on the perspectives of the different activation modes made available by this catalytic system. Starting with a short introduction to aminocatalysis, we will outline the properties that have made the diarylprolinol silyl ethers a common choice of catalyst. Furthermore, we will describe the major tendencies in the activation and reaction concepts developed with regard to reactivity patterns and combinations with other activation concepts. Looking back—don′t look back: After ten years of asymmetric organocatalysis with diarylprolinol silyl ethers, we look back over the history of this class of aminocatalysts and its impact. We outline the development of this area from reactions via enamine and iminium ion intermediates to remote functionalizations, combinatorial methods, and industrial applications, describing in which directions these catalysts have moved organocatalysis and where the field might be going.