Highly Selective Synthesis of cis-Enediynes on a Ag(111) Surface

Abstract

Cis-enediyne-type compounds have received much attention as potent antitumor antibiotics. The conventional synthesis of cis-enediynes in solution typically involves multiple steps and various side reactions. For the first time, selective one-step synthesis of cis-enediyne from a single reactant is reported on a Ag(111) surface with a yield up to 90 %. High selectivity for the formation of cis-enediyne originates from the steric effect posed by weak intermolecular interactions, which protect the cis-enediyne from further reaction. A series of comparative experiments and DFT-based transition-state calculations support the findings. The described synthetic approach for directing reaction pathways on-surface may illuminate potential syntheses of other unstable organic compounds.

Keywords: cis-enediyne; hydrogen bonds; on-surface synthesis; steric effect; terminal alkynes.