Directing-group-free catalytic dicarbofunctionalization of unactivated alkenes

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.

Automated summary

This study presents a new directing-group-free, nickel-catalysed strategy for the catalytic addition of carbogenic groups to unactivated and activated olefins with control of regioselectivity, achieving up to 93% yield and >98% site selectivity. The method can be extended to other types of reactions by switching reagents, and mechanistic and computational investigations provide insights into the regiochemical outcome of the reaction. The utility of the method is demonstrated through the concise syntheses of biologically active molecules, and the reported catalyst control principles are expected to advance efforts towards developing general site-selective alkene functionalizations.