Catalytic and Enantioselective Diels‐Alder Reaction of Siloxydienes

Abstract Diels‐Alder reaction is one of the most well‐known named reactions in organic chemistry. It involves a diene substrate and a dienophile substrate. Among dienes, siloxydiene is a reactive substrate that is often used in Diels‐Alder reaction. In general, Diels‐Alder reaction is promoted by an acidic reagent. In many cases, the stereoselectivity of the reaction is also controlled by acids. However, siloxydienes are labile under acidic conditions. Thus, it should be difficult to develop a reaction using siloxydiene as a substrate. Nevertheless, siloxydienes are still used in synthetic organic chemistry, and most reactions are performed under thermal activation conditions. In this minireview, we summarize the reported examples of catalytic and enantioselective Diels‐Alder reactions of siloxydienes based on the structure of the diene. We present the activation methods used, the existing problems, and a clue for the further development of this annulation chemistry.