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.

doi:10.1002/ejoc.202201005

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.

Authors

Mingyan Ding

Jonathan A. Reuven

Andrew C. Hones

Dr Mark Fox m.a.fox@durham.ac.uk
Assistant Professor

Professor Patrick Steel p.g.steel@durham.ac.uk
Professor

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

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