Gold(I)-Catalyzed 1,6-Enyne Single-Cleavage Rearrangements: The Complete Picture

We identify the factors that rule the selectivity insingle-cleavageskeletal rearrangements promoted by gold(I) catalysts. We find thatstereoconvergence is enabled by a rotational equilibrium when electron-richsubstituents are used. The anomalous Z-selectiveskeletal rearrangement is found to be due to electronic factors, whereas endo-selectivity depends on both steric and electronic factors.

Automated summary

This study identifies the factors influencing the selectivity in single-cleavage skeletal rearrangements promoted by gold(I) catalysts. It is found that stereoconvergence is achieved through a rotational equilibrium when electron-rich substituents are utilized. The anomalous Z-selective skeletal rearrangement is primarily governed by electronic factors, while endo-selectivity relies on both steric and electronic factors.