Radical chemistry of nitrosoarenes: concepts, synthetic applications and directions

Abstract

Nitrosoarenes are readily available and highly reactive, making them promising building blocks in organic chemistry. The recent development of radical conversions of nitrosoarenes provides an alternative and powerful platform for...

Azodioxy compounds as precursors for C-radicals and their application in thermal styrene difunctionalization

“… 16 However, their synthetic utility in chemistry has so far mostly been limited to the role as C radical acceptors. 17 Nonetheless, we demonstrated in this initial study their promising potential as C-radical precursors. 13 However, it is well established that the majority of the C-nitroso compounds are not stable in solution and dimerize to the corresponding azodioxy compounds.…”

Photo‐Mediated Intermolecular Coupling of Alkenes with Ketones via Acyloxy Nitroso Compounds

“…The oximes in turn are readily accessed by condensing a ketone with hydroxylamine. Notably, C‐nitroso compounds have been widely used as C radical acceptors; however, their potential as C radical precursors is not explored [11] . We decided to use acyloxy nitroso compounds as C radical precursors to react with electron‐deficient alkenes.…”

“…Notably, C-nitroso compounds have been widely used as C radical acceptors; however, their potential as C radical precursors is not explored. [11] We decided to use acyloxy nitroso compounds as C radical precursors to react with electron-deficient alkenes. Visible-light-induced CÀNO bond homolysis should lead to an electron-rich transient C radical and the persistent NO radical in a reversible process.…”

Licht‐vermittelte intermolekulare Kupplung von Alkenen mit Ketonen über Acyloxy‐Nitroso‐Verbindungen

“…Die Oxime wiederum sind durch Kondensation eines Ketons mit Hydroxylamin leicht zugänglich. Insbesondere C‐Nitroso‐Verbindungen sind als C‐Radikal‐Akzeptoren weit verbreitet; ihr Potenzial als C‐Radikal‐Vorläufer ist jedoch nicht erforscht [11] . Wir entschieden uns, Acyloxy‐Nitroso‐Verbindungen als C‐Radikal‐Vorläufer für die Reaktion mit elektronenarmen Alkenen zu verwenden.…”

“…Insbesondere C-Nitroso-Verbindungen sind als C-Radikal-Akzeptoren weit verbreitet; ihr Potenzial als C-Radikal-Vorläufer ist jedoch nicht erforscht. [11] Wir entschieden uns, Acyloxy-Nitroso-Verbindungen als C-Radikal-Vorläufer für die Reaktion mit elektronenarmen Alkenen zu verwenden. Die durch sichtbares Licht induzierte Homolyse der C-NO-Bindung sollte in einem reversiblen Prozess zu einem elektronenreichen transienten C-Radikal und dem persistenten NO-Radikal führen.…”