Insights into the Gold‐Catalyzed Cycloisomerization of 3‐Allyl‐1,4‐diynes for the Synthesis of Bicyclic Hydrocarbons.

An efficient protocol for the synthesis of 3‐ethynyl‐2‐aryl‐bicyclo[3.1.0]hexenes through a gold‐catalyzed enyne cyclization was established in this work. Depending on the specific substitution pattern, unusual cationic rearrangements of the corresponding gold carbene were revealed, leading to either cyclohexadienes or 5,9‐methanobenzo[8]annulene derivatives, respectively. [ABSTRACT FROM AUTHOR]