Product‐Catalyzed Aldol Reaction between Trimethylsilyl Enolates and Aldehydes

Aldol reactions between trimethylsilyl ketene acetals and aldehydes by using a catalytic amount of alkoxide anion proceeded smoothly to afford the corresponding aldols in DMF, indicating that the initially‐formed aldolate anion effectively worked to catalyze the reaction. The “product‐catalyzed aldol reaction”, a new class Lewis base‐catalyzed aldol reaction, between trimethylsilyl ketene acetals and aldehydes was performed successfully by the use of aldolate anion as a Lewis base catalyst.