Synthetic and mechanistic studies into the reductive functionalization of nitro compounds catalyzed by an Iion(salen) complex

Pocock, Emily, Diefenbach, Martin, Hood, Thomas M., Nunn, Michael, Richards, Emma ORCID: https://orcid.org/0000-0001-6691-2377, Krewald, Vera and Webster, Ruth L. 2024. Synthetic and mechanistic studies into the reductive functionalization of nitro compounds catalyzed by an Iion(salen) complex. Journal of the American Chemical Society 146 (29) , pp. 19839-19851. 10.1021/jacs.4c02797

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Abstract

We report on the use of a simple, bench-stable [Fe(salen)2]-μ-oxo precatalyst in the reduction of nitro compounds. The reaction proceeds at room temperature across a range of substrates, including nitro aromatics and aliphatics. By changing the reducing agent from pinacol borane (HBpin) to phenyl silane (H3SiPh), we can chemoselectively reduce nitro compounds while retaining carbonyl functionality. Our mechanistic studies, which include kinetics, electron paramagnetic resonance (EPR), mass spectrometry, and quantum chemistry, indicate the presence of a nitroso intermediate and the generation of an on-cycle iron hydride as a key catalytic intermediate. Based on this mechanistic insight, we were able to extend the chemistry to hydroamination and identified a simple substrate feature (alkene lowest unoccupied molecular orbital (LUMO) energy) that could be used to predict which alkenes would result in productive catalysis.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	American Chemical Society
ISSN:	0002-7863
Funders:	EPSRC, Leverhulme Trust and Astra Zeneca
Date of First Compliant Deposit:	24 July 2024
Date of Acceptance:	25 June 2024
Last Modified:	25 Jul 2024 14:00
URI:	https://orca.cardiff.ac.uk/id/eprint/170891

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