<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Enantiopure SPINOL‐phosphoric acids exhibit high activities and excellent diastereo‐ and enantioselectivities in the catalysis of the three‐component Povarov reaction of N‐vinylcarbamate (III), anilines (II) and aldehydes (I).</p> </abstract>