Chiral Hydrogen-Bond Donor and Gold(I) Cocatalysis Enables Enantioselective Dearomative Spirocyclization of Naphthols
Year: 2025
Type: article
Abstract: We report the enantioselective gold(I)-catalyzed dearomative spirocyclization of naphthols enabled by the cooperative effect of chiral dual hydrogen-bond donors (HBDs). The reaction affords carbocyclic and heterocyclic spirocycles bearing a quaternary stereocenter with high enantioselectivity (up to 99% enantiomeric excess). Kinetic analysis supports a mode of catalysis wherein two molecules of a monomeric urea cocatalyst activate the neutral gold(I) sulfonate complex via anion abstraction to induce enantioselectivity and rate acceleration in the cyclization reaction. A systematic investigation of ligand effects identified a correlation between the electronic properties of the gold(I) phosphine ligand and the observed enantioselectivity.
DOI: 10.1021/jacs.5c15891
Authors: Timur Adrianov, Eric N. Jacobsen
Institution: Harvard University
Language: English
Topic: Catalytic Alkyne Reactions
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Awards: G1300660318, G248837153
OpenAlex ID: W4415630026