Iridium‐Catalysed C−H Borylation of Fluoroarenes: Insights into the Balance between Steric and Electronic Control of Regioselectivity

Ding, Mingyan; Reuven, Jonathan A.; Hones, Andrew C.; Fox, Mark A.; Steel, Patrick G.

Abstract

The iridium catalysed C−H borylation of polyfluorinated arenes and heteroarenes occurs rapidly and efficiently. As with other borylation reactions, whilst steric parameters dominate, an underlying electronic influence on reaction selectivity can be observed. Notably borylation regioselectivity in fluorinated (hetero)arenes is determined by purely electronic effects except for ortho-borylation between two fluorine atoms where steric effects of fluorine substituents become apparent. Borylation at the para position with respect to fluorine is disfavoured whereas a strong electronic preference for borylation para to the azinyl nitrogen of pyridine is observed. When these features co-operate high selectivity can be expected. For these reactions, computations based on transition state, rather than intermediate, energies in iridium geometries showed excellent agreement between predicted and observed selectivities.

Citation

Ding, M., Reuven, J. A., Hones, A. C., Fox, M. A., & Steel, P. G. (2022). Iridium‐Catalysed C−H Borylation of Fluoroarenes: Insights into the Balance between Steric and Electronic Control of Regioselectivity. European Journal of Organic Chemistry, 2022(47), https://doi.org/10.1002/ejoc.202201005

• Journal Article Type: Article
• Online Publication Date: Dec 16, 2022
• Publication Date: 2022-12
• Deposit Date: Dec 16, 2022
• Publicly Available Date: Dec 16, 2022
• Journal: European Journal of Organic Chemistry
• Print ISSN: 1434-193X
• Electronic ISSN: 1099-0690
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 2022
• Issue: 47
• DOI: https://doi.org/10.1002/ejoc.202201005
• Public URL: https://durham-repository.worktribe.com/output/1185001