Mechanistic Study on Selenium- and Sulfur-Mediated Isomerization of Hydroxamic Acids

Ricardo Meyrelles; Manuel Schupp; Boris Maryasin

doi:10.1002/chem.202302386

Mechanistic Study on Selenium- and Sulfur-Mediated Isomerization of Hydroxamic Acids

Chemistry. 2023 Dec 19;29(71):e202302386. doi: 10.1002/chem.202302386. Epub 2023 Nov 5.

Authors

Ricardo Meyrelles^{1

2

3}, Manuel Schupp^{1

3

4}, Boris Maryasin^{1

2}

Affiliations

¹ Institute of Organic Chemistry, Faculty of Chemistry, University of Vienna, Währinger Straße 38, 1090, Vienna, Austria.
² Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna, Währinger Straße 17, 1090, Vienna, Austria.
³ Vienna Doctoral School in Chemistry, University of Vienna, Währinger Straße 42, 1090, Vienna, Austria.
⁴ CeMM Research Center for Molecular Medicine, Austrian Academy of Sciences, Lazarettgasse 14, AKH BT 25.3, 1090, Vienna, Austria.

PMID: 37769009
DOI: 10.1002/chem.202302386

Abstract

An in-depth computational study reveals the intriguing mechanism of the recently reported isomerization of hydroxamic acids into para-aminophenols catalyzed by phenylselenyl bromide under mild conditions. The computations not only align with the reported experimental data, effectively explaining observed phenomena such as para-selectivity but also shed light on crucial aspects of the reaction mechanism that establish limitations on the scope of the studied rearrangement. Additionally, a joint theoretical/experimental study was performed to examine the potency of the phenylsulfenyl bromide to mediate the reaction under the same conditions.

Keywords: DFT; organoselenium; organosulfur; reaction mechanism; sigmatropic rearrangement.