Au-Catalyzed Hexannulation and Pt-Catalyzed Pentannulation of Propargylic Ester Bearing a 2-Alkynyl-phenyl Substituent: A Comparative DFT Study.

The mechanistic pathways of metal-catalyzed pentannulation and hexannulation of aromatic enediyne were studied quantum mechanically with Pt and Au salts. In agreement with the experimental facts, our result shows that the pentannulation favors over the hexannulation under Pt-catalyzed conditions and the reverse possibility favors when the Pt salt is replaced with an Au one. The Pt-catalyzed reaction involves a long-range acyl migration that follows the cyclization step. Our study reveals that such migration takes place under the assistance of a ligand of the metal atom. Moreover, the variation of aromaticity (probed by the change of the nucleus-independent chemical shift (0) value) in the cyclization steps shows that both processes maintain the development of the aromatic character of the generated intermediate during the progress of the reaction.