Saper NI,
Ohgi A,
Small DW,
Semba K,
Nakao Y.
*
Hartwig JF.
* University of California, Berkeley, USA; Kyoto University, Japan
Nickel-Catalysed anti-Markovnikov Hydroarylation of Unactivated Alkenes with Unactivated Arenes Facilitated by Non-Covalent Interactions.
Nat. Chem. 2020;
12: 276-283
Key words
nickel catalysis - C–H activation - hydroarylation - unactivated alkenes - anti-Markovnikov reaction
Significance
Nakao, Hartwig and co-workers report a novel nickel-catalyzed undirected hydroarylation reaction between unactivated alkenes and unactivated arenes. The reaction proceeds in excellent yields with high selectivity for the anti-Markovnikov product. These products are distinct from those accessed through acid-catalyzed processes.
Comment
The authors characterized the catalytically relevant substrate bound nickel complexes and identified the reductive elimination step forming the C–C bond as the rate-limiting step. They also note that differences in the activity between catalysts with large/small carbenes are more dependent on the stabilizing intramolecular noncovalent interactions in the secondary coordination sphere, than steric hindrance.
