Homogeneous gold catalysis has emerged as a powerful tool in organic synthesis, owing to the unique ability of cationic gold complexes to activate unsaturated bonds. Over the past decades, gold(I)-catalyzed reactions have been widely applied to access complex molecular frameworks, particularly in the total synthesis of natural products. This lecture will first highlight the development of new chiral phosphines and their applications in enantioselective cycloisomerizations.[1-4] Recent advances in gold catalysis will then be presented, with a particular focus on the synthesis of cyclopentenones bearing C4-quaternary stereocenters through a stereospecific gold(I)-catalyzed sulfonium [3,3]-sigmatropic rearrangement of vinyl sulfoxides. This straightforward asymmetric methodology has enabled the total synthesis of several natural sesquiterpenoids, as well as myrmenaphthol A, a natural product recently isolated from a Hawaiian sponge.[5-9]
[1] ACS Catal. 2020, 10, 8141; [2] Adv. Synth. Catal. 2022, 364, 4415; [3] Chem. Commun. 2022, 58, 3043; [4] Adv. Synth. Catal. 2025, e202401541; [5] J. Am. Chem. Soc. 2021, 143, 17348; [6] Org. Lett. 2021, 23, 247; [7] Org. Chem. Front. 2024, 11, 6804; [8] Org. Lett. 2024, 26, 6637; [9] ChemistryEurope 2026, e202500274.