Bifunctional Phosphine-Enabled Regioselective Cycloisomerization of Enynyl Esters En Route to Bicyclo[2.2.1]heptenes.

Expedient access to bridged enol benzoates is realized via a tandem gold-catalyzed cycloisomerization of enynyl esters and the Diels-Alder reaction. The gold catalysis permits the use of enynyl substrates without additional propargylic substitution and achieves the highly regioselective formation of less stable cyclopentadienyl esters. The regioselectivity is enabled by a bifunctional phosphine ligand, the remote aniline group of which facilitates α-deprotonation of a gold carbene intermediate. The reaction works with different alkene substitution patterns and various dienophiles.