On the Structure of Intermediates in Enyne Gold(I)‐Catalyzed Cyclizations: Formation of trans ‐Fused Bicyclo[5.1.0]octanes as a Case Study

The nature of cyclopropyl gold(I) carbene‐type intermediates has been reexamined as part of a mechanistic study on the formation of cis‐ or trans‐fused bicyclo[5.1.0]octanes in a gold(I)‐catalyzed cascade reaction. Benchmark of DFT methods together with QTAIM theory and NBO analysis confirms the formation of distinct intermediates with carbenic or carbocationic structures in the cycloisomerizations of enynes.
Going for gold: The nature of cyclopropyl gold(I) carbene‐type intermediates has been explored as part of a mechanistic study on the gold(I)‐catalyzed formation of trans‐fused bicyclo[5.1.0]octanes. Complete computational analysis, that includes QTAIM theory and NBO analysis, confirms the formation of different species with carbenic or cationic nature as intermediates in the cycloisomerizations of enynes.