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A selenium‐catalysed para‐hydroxylation of N‐aryl‐hydroxamic acids is reported. Mechanistically, the reaction comprises an N−O bond cleavage and consecutive selenium‐induced [2,3]‐rearrangement to deliver para‐hydroxyaniline derivatives. The mechanism is studied through both 18O‐crossover experiments as well as quantum chemical calculations. This redox‐neutral transformation provides an unconventional synthetic approach to para‐aminophenols. [ABSTRACT FROM AUTHOR]

A new approach to prepare α-selanyl-α,β-unsaturated thioesters from propargylthioalkynes and an electrophilic selenium species is reported. Pivotal is the intermediacy of a sulfur-stabilized vinyl cation, which is captured intramolecularly and ultimately enables 37 examples of the target compounds to be prepared in good yields. Computational studies shed light on the nature of intermediates in this transformation. [ABSTRACT FROM AUTHOR]

Although a fairly large number of binary group 15/16 element cations have been reported, no example involving phosphorus in combination with a group 16 element has been synthesized and characterized to date. In this contribution is reported the synthesis and structural characterization of the first example of such a cation, namely a nortricyclane-type [P3Se4]+. This cation has been independently discovered by three groups through three different synthetic routes, as described herein. The molecular and electronic structure of the [P3Se4]+ cage and its crystal properties in the solid state have been characterized comprehensively by using X-ray diffraction, Raman, and nuclear magnetic resonance spectroscopies, as well as quantum chemical calculations. [ABSTRACT FROM AUTHOR]

[2,3]-rearrangement, aminophenol, hydroxamic acid, N-O bond cleavage, selenium Frontispiece: Redox-Neutral Selenium-Catalysed Isomerisation of para-Hydroxamic Acids into para-Aminophenols Keywords: [2,3]-rearrangement; aminophenol; hydroxamic acid; N-O bond cleavage; selenium EN [2,3]-rearrangement aminophenol hydroxamic acid N-O bond cleavage selenium 1 1 1 06/09/21 20210614 NES 210614 B Organic Synthesis b In their Communication on page 13778, Boris Maryasin, Nuno Maulide et al. report the selenium-catalysed redox isomerisation of hydroxamic acids into I para i -aminophenols. [Extracted from the article]