Gold(I)‐Catalyzed Enantioselective Cycloisomerization of 1,6‐Oxygenated Enynes: An Entry to Hedonic Derivatives

A highly efficient gold(I)‐catalyzed enantioselective cycloisomerization of readily available 1,6‐oxygenated enynes is reported, enabling direct access to valuable 3‐oxabicyclo[4.1.0]hept‐4‐ene scaffolds with excellent enantiomeric excesses (up to >99% ee, 35 derivatives), in the presence of a chiral cationic Au(I) catalyst (( S )‐DTBM‐MeOBIPHEP(AuCl) 2 /AgOTf system) in toluene. This methodology uniquely combines high stereoselectivity with good to excellent yields for volatile substrates that have been challenging derivatives in the asymmetric cycloisomerization community. Notably, the resulting chiral bicyclic ethers serve as versatile intermediates for the synthesis of novel hedonic derivatives. A systematic investigation of their odor profiles reveals remarkable differences between enantiomers, demonstrating the profound impact of molecular chirality on olfactory perception.