Nickel-catalyzed intermolecular oxidative Heck arylation driven by transfer hydrogenation.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 31690717.
- Also identified by DOI 10.1038/s41467-019-12949-1 and PMC identifier 6831602.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
The conventional oxidative Heck reaction between aryl boronic acids and alkenes typically involved the Pd<sup>II</sup>/Pd<sup>0</sup>/Pd<sup>II</sup> catalytic cycle incorporating an external oxidant and often suffered C=C bond isomerization for internal alkyl-substituted alkenes via chain-walking. Herein, we demonstrate that the regioselectivity (γ-selectivity vs. δ-selectivity) and pathway selectivity (hydroarylation vs. oxidative Heck coupling) of a directed Ni-catalyzed alkene arylation can be controlled by judicious tuning of the coordination environment around the nickel catalyst via optimization of an appropriate phosphine ligand and directing group. In this way, the Ni(0)-catalyzed oxidative Heck arylation that relies on transfer hydrogenation of an acceptor olefin is developed with excellent E/Z selectivity and regioselectivity. Mechanistic investigations suggest that the addition of the acceptor is crucial for lowering the energy for carbometalation and for enabling catalytic turnover.