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.
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