Catalytic isomerization of 1,5-enynes to bicyclo[3.1.0]hexenes

The cycloisomerization of 1,5-enynes catalyzed by cationic triphenylphosphinegold(I) complexes produces bicyclo3.1.0]hexenes. Substitution at all positions of the 1,5-enyne is tolerated, leading to a wide range of bicyclo3.1.0]hexane structures, including those containing quaternary carbons. Substrates containing a 1,2-disubstituted olefin undergo stereospecific cycloisomerization (cis-olefin produces cis-cyclopropane, and trans-olefin gives trans-cyclopropane). Additionally, enantioenriched bicyclo3.1.0]hexenes can be obtained from the gold(I)-catalyzed cycloisomerization of enantioenriched 1,5-enynes with excellent chirality transfer. The preparation of tricyclic systems is accomplished through a gold(I)-catalyzed tandem cycloisomerization-ring enlargement reaction.