Document Type
Article
Publication Date
8-16-2024
Publication Title
The Journal of Organic Chemistry
Abstract
We report the mechanism of the iron-catalyzed oxidative α-amination of ketones with sulfonamides. Using linear free energy relationships, competition experiments, and identification of reaction intermediates, we have found that the mechanism of this reaction proceeds through rate-limiting electron transfer to 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) from an iron enolate in the process of forming an α-DDQ adduct. The adduct then serves as the electrophile for substitution with sulfonamide nucleophiles, accelerated by iron and additional DDQ. This mechanistic study rules out formation of an α-carbocation intermediate and purely radical mechanistic hypotheses.
Keywords
Adducts, Iron, Ketones, Substitution Reactions, Sulfones
DOI
10.1021/acs.joc.4c01401
Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.
Rights
© 2024 The Authors.
Recommended Citation
Parrales, Gloria M.; Hollin, Nina C.; Song, Fubin; Lyu, Yangyang; Martin, Anne-Marie O.; and Strom, Alexandra E., "Mechanism of Iron-Catalyzed Oxidative α-Amination of Ketones with Sulfonamides" (2024). Chemistry: Faculty Publications, Smith College, Northampton, MA.
https://scholarworks.smith.edu/chm_facpubs/92
Comments
Archived as published.