Enantioselective Alkynylbenzaldehyde Cyclizations Catalyzed by Chiral Gold(I) Acyclic Diaminocarbene Complexes Containing Weak Au–Arene Interactions

Hold me close: Highly enantioselective catalysis of tandem acetalization/cycloisomerization reactions of o‐alkynylbenzaldehydes has been achieved using gold complexes of chiral acyclic diaminocarbene ligands that have electron‐deficient aryl substituents. X‐ray crystallography and DFT calculations implicate weak gold‐arene interactions—absent in the case of simple phenyl substituents—that define the chirality of the substrate binding site.