Oxidative addition of an alkyl halide to form a stable Cu(III) product.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 37676952.
- Also identified by DOI 10.1126/science.adg9232 and PMC identifier 10658983.
- No licence information is recorded for this record.
- Because redistribution is not established, this page shows the abstract only. Follow the links below for the full text.
Abstract
The step that cleaves the carbon-halogen bond in copper-catalyzed cross-coupling reactions remains ill defined because of the multiple redox manifolds available to copper and the instability of the high-valent copper product formed. We report the oxidative addition of α-haloacetonitrile to ionic and neutral copper(I) complexes to form previously elusive but here fully characterized copper(III) complexes. The stability of these complexes stems from the strong Cu-CF<sub>3</sub> bond and the high barrier for C(<i>CF<sub>3</sub></i>)-C(<i>CH<sub>2</sub>CN</i>) bond-forming reductive elimination. The mechanistic studies we performed suggest that oxidative addition to ionic and neutral copper(I) complexes proceeds by means of two different pathways: an S<sub>N</sub>2-type substitution to the ionic complex and a halogen-atom transfer to the neutral complex. We observed a pronounced ligand acceleration of the oxidative addition, which correlates with that observed in the copper-catalyzed couplings of azoles, amines, or alkynes with alkyl electrophiles.