Directed Markovnikov hydroarylation and hydroalkenylation of alkenes under nickel catalysis

We report a full account of our research on nickel-catalyzed Markovnikov-selective hydroarylation and hydroalkenylation of non-conjugated alkenes, which has yielded a toolkit of methods that proceed under mild conditions with alkenyl sulfonamide, ketone, and amide substrates

Zi-Qi Li; Omar Apolinar; Ruohan Deng; Keary M. Engle

2021

Scholarcy highlights

  • Catalytic alkene functionalization is an efficient and economical way to build up molecular complexity from readily accessible chemical feedstocks
  • A notable advance was reported by Shenvi and co-workers 2016, who developed a dual-catalytic Co/Ni metal–hydride H-atomtransfer approach that was effective for the hydroarylation of terminal alkenes with aryl halides, where regioselectivity is controlled by the favorable formation of a secondary alkyl radical via MHAT.13c
  • It is worth mentioning that even though we screened a wide breadth of different ligands, there was no sign of ligand-based regiodivergence as was reported with alkenyl carboxylates
  • In a kinetic isotope effect experiment, we found vH/vD 1⁄4 1.23, suggesting that hydrometallation might not be involved in the
  • When alkenyl ketone was used as substrate, a larger energy barrier was observed, which explains the higher regioselectivity obtained experimentally
  • A computational study revealed that the directing-group-controlled formation of a ve-membered alkyl nickel species is the origin of high Markovnikov selectivity

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