Directing-group-free catalytic dicarbofunctionalization of unactivated alkenes. Academic Article uri icon


  • In the absence of directing auxiliaries, the catalytic addition of carbogenic groups to unactivated alkenes with control of regioselectivity remains an ongoing challenge in organic chemistry. Here we describe a directing-group-free, nickel-catalysed strategy that couples a broad array of unactivated and activated olefins with aryl-substituted triflates and organometallic nucleophiles to afford diarylation adducts in either regioisomeric form, in up to 93% yield and >98% site selectivity. By switching the reagents involved, the present strategy may be extended to other classes of dicarbofunctionalization reactions. Mechanistic and computational investigations offer insights into the origin of the observed regiochemical outcome and the utility of the method is highlighted through the concise syntheses of biologically active molecules. The catalyst control principles reported are expected to advance efforts towards the development of general site-selective alkene functionalizations, removing the requirement for neighbouring activating groups.

published proceedings

  • Nat Chem

author list (cited authors)

  • Wang, H., Liu, C., Martin, R. T., Gutierrez, O., & Koh, M. J.

complete list of authors

  • Wang, Hongyu||Liu, Chen-Fei||Martin, Robert T||Gutierrez, Osvaldo||Koh, Ming Joo

publication date

  • January 2022