Chiral gold(I)‐cavitand complexes have been developed for the enantioselective alkoxycyclization of 1,6‐enynes. This enantioselective cyclization has been applied for the first total synthesis of carbazole alkaloid (+)‐mafaicheenamine C and its enantiomer, establishing its configuration as R. The cavity effect was also evaluated in the cycloisomerization of dienynes. A combination of experiments and theoretical studies demonstrates that the cavity of the gold(I) complexes forces the enynes to adopt constrained conformations, which results in the high observed regio‐ and stereoselectivities.

Chiral gold(I)‐cavitand complexes have been developed for the enantioselective alkoxycyclization of 1,6‐enynes. This enantioselective cyclization has been applied for the first total synthesis of carbazole alkaloid (+)‐mafaicheenamine C and its enantiomer, establishing its configuration as R. The cavity effect was also evaluated in the cycloisomerization of dienynes. A combination of experiments and theoretical studies demonstrates that the cavity of the gold(I) complexes forces the enynes to adopt constrained conformations, which results in the high observed regio‐ and stereoselectivities.

The enantioselective reaction of 1,6-enynes with O-, N-, and C-nucleophiles has been developed by matched ion pair gold(I) catalysis in which the chiral gold(I) cation and anion are H-bonded through a urea group. Very high levels of enantiocontrol are achieved (up to >99:1 er) for a broad scope of substrates. DFT studies demonstrate the importance of the H-bond donor group in anchoring the matched chiral cation- and anion-favoring additional noncovalent interactions.