1,2-Difunctionalization of Acetylene Enabled by Light

Angew Chem Int Ed Engl. 2023 Apr 11;62(16):e202300268. doi: 10.1002/anie.202300268. Epub 2023 Mar 13.


Although the direct conversion of gaseous acetylene into value-added liquid commodity chemicals is becoming increasingly attractive, the majority of the established methodologies are focused on cross-coupling, hydro-functionalization, and polymerization. Herein, we describe a 1,2-difunctionalization method that inserts acetylene directly into readily available bifunctional reagents. This method provides access to diverse C2-linked 1,2-bis-heteroatom products in high regio- and stereoselectivity along with opening up previously unexplored synthetic directions. In addition, we demonstrate this method's synthetic potential by converting the obtained products into diverse functionalized molecules and chiral sulfoxide-containing bidentate ligands. Using a combination of experimental and theoretical methods, the mechanism for this insertion reaction was investigated.

Keywords: 1,2-Difunctionalization; Acetylene; Olefins; Photochemistry; Radical Chemistry.