A General and Efficient Method To Convert Selenides into Selenones by Using HOF·CH₃CN

Abstract

A general route for the preparation of selenones (R2SeO2) is presented. This task is achieved through the quick and high‐yielding reaction of selenides (R2Se) with HOF·CH3CN. The reaction tolerates some elusive electron‐deficient and sterically hindered selenides. Some mechanistic aspects are also investigated and discussed.

Oxone‐Mediated Oxidation of Vinyl Selenides in Water

“…Diphenyl Selenone (3q): , The crude product was purified by chromatography (eluent: dichloromethane/methanol = 99:1) to afford 3q as a colorless solid (m.p. 141–142 °C) in 80 % yield.…”

“…Hydrogen peroxide with catalytic amounts of benzenseleninic acid and inorganic oxidants such as potassium permanganate or Oxone are also suitable for the oxidation. Two procedures employing the HOF · CH 3 CN complex prepared by bubbling dilute F 2 into aqueous acetonitrile and the HMPA molybdenum complex [MoO(O) 2 (H 2 O)(HMPA)] have been developed recently. All these methods show drawbacks in terms of safety, cost, waste, or use of heavy metals or halogenated solvents.…”

Modern Synthetic Strategies with Organoselenium Reagents: A Focus on Vinyl Selenones

“…The first oxidation of selenides to selenoxides is fast, but the decreased electron density on the selenium atom makes selenoxides less prone to the second oxygen transfer. Even if, several strong oxidants convert selenides into selenones, i.e., KMnO 4 [6], peroxyacids or their salts [6,7], H 2 O 2 in the presence of benzenseleninic acid [8], HMPA peroxo complex of molybdenum [9], Oxone ® [10], and HOF•CH 3 CN complex [11], 3-chloroperoxybenzoic acid (m-CPBA) [12] is the reagent of choice for the oxidation of vinyl selenides (Scheme 1, route a). It is used in excess in alcoholic, ethereal or halogenated solvents.…”

Bis(2,6-diisopropylphenyl) tellurone: a well-defined monomeric diorganotellurone without cocrystallized solvents and without stabilizing intramolecular contacts

“…Compared to their lighter Group 16 analogues, the chemistry of organotellurium compounds is still in its early stage of development (Srivastava et al, 2018;Rappoport et al, 2014). Even the structure of diorganotellurones has not been well understood, despite extensive studies on the corresponding sulfones (Liu et al, 2016;Magnus, 1977;Patai et al, 1988) and selenones (Krief et al, 1985;Palomba et al, 2021;Potash & Rozen, 2013). The primary reason is that tellurones exist as a random polymeric mixture due to the intermolecular interactions of the strongly polarized Te-O bonds.…”