The Diarylprolinol Silyl Ethers: After 20 Years Still Opening New Doors in Asymmetric Catalysis

A new chapter starts now . Since its discovery in 2005, the diarylprolinol silyl ether catalytic concept has emerged as a general and reliable aminocatalytic tool for the synthesis of enantioenriched molecules. Recently its combination with emerging technologies, as well as its application in more complex molecular systems has opened new avenues for novel enantioenriched scaffolds. In this review, we will highlight these recent developments, unfolding five primary categories that define new horizons in the use of diarylprolinol silyl ethers: Photochemical‐, electrochemical‐, dual‐catalytic transformations, higher‐order cycloadditions and applications in total synthesis of complex natural products.