In the first of a two-paper installment (stay tuned for the second!), we document how the unique hemilabile and redox-active properties of quinone ligands can enable otherwise challenging nickel-catalyzed alkene functionalization reactions. In particular, we show dramatic ligand-enabled expansion of the scope of our previously developed syn-1,2-carbosulfenylation reaction of unactivated alkenes to include a variety of N–S(Alkyl) electrophiles and alkyl- and alkenylboron nucleophiles that were previously recalcitrant. Important mechanistic insights from DFT and structural characterization came through the awesome collaboration with Turki (University of Pittsburgh) and Matt (Bristol Myers Squibb), shed light on the hemilabile and redox-active nature of the ligand in the catalytic cycle. We expect that this mechanistic framework should pave the way for numerous advances in the future. Congrats to project lead Zi-Qi and the entire team!

For a link to the pre-print in ChemRxiv, click here: https://chemrxiv.org/engage/chemrxiv/article-details/6544308648dad23120f59b66