Regioselective Twofold Annulation of Propargyl Acetates.

The regioselective annulation of unsymmetrical alkynes has always been a focused research topic. A Pd-catalyzed double annulation of unsymmetrical alkynes (i.e., yne-acetates) with aryl diazonium salts for the synthesis of substituted naphthalene derivatives is developed. The process addresses intrinsic regioselectivity challenges in the annulations of unsymmetrical alkynes. Mechanistic investigations shed light on the crucial role of the acetate-directing groups in determining the regiochemical reaction outcome.