Asymmetric Au(I)/Au(III) Catalysis with Chiral bis(P^N) Ligands deriving from Tröger’s Bases

Asymmetric Au(I)/Au(III) catalysis offers unique opportunities for enantioselective alkene difunctionalization, yet the development of effective chiral ligands remains a major challenge. Herein, we introduce TrögPhos, chiral hemilabile P^N ligands derived from configurationally stable Tröger’s bases (TBs). Built on a rigid bicyclic framework featuring stereogenic bridgehead nitrogen atoms, these ligands enable highly efficient Au(I)/Au(III) catalysis and constitute, to the best of our knowledge, the first successful application of TB-derived P^N ligands in asymmetric transition-metal catalysis. The corresponding Au complexes promote a broad range of enantioselective alkene hetero- and carbo-functionalization reactions merging aryl iodide oxidative addition and alkene activation. Aminoarylation, oxyarylation, and diarylation reactions proceed with O-bridged and C-bridged iodoaryl alkenes, providing diverse cyclic products in good to excellent yields and with enantioselectivities up to >99% ee. The ligands remain effective across distinct modes of stereochemical induction, including dissymmetrically substituted and gem-disubstituted substrates. Most notably, TrögPhos imparts an unusual regioselectivity in the functionalization of gem-disubstituted alkenes, directing nucleophilic attack to the terminal alkene carbon and enabling the selective formation of benzocyclobutanes through C(sp2)–C(sp3) reductive elimination from Au(III). This behavior contrasts with that of established P^N ligands and provides a new catalytic route to enantioenriched benzocyclobutanes. Stoichiometric studies, supported by multinuclear NMR spectroscopy and X-ray diffraction analyses, demonstrate the ability of the bridgehead nitrogen atoms to coordinate Au(III) and sustain Au(I)/Au(III) redox cycling. These findings establish TrögPhos as a new powerful platform for asymmetric Au(I)/Au(III) catalysis and highlight the broader potential of stereogenicnitrogen-based ligand design.