Reaction of a free organic radical with grignard reagent

Rozantsev, É. G.; Neiman, M. B.; Mamedova, Yu. G.

doi:10.1007/bf00847814

Cited by 1 publication

(2 citation statements)

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“…The keto functionality in nitroxide 8 can be readily chemically modified without destroying its radical character. Thus, hydrazone formation, , Grignard addition, , hydride reduction, Wolff–Kishner reduction, Beckmann rearrangement, and Stobbe condensation were achieved with the nitroxide moiety remaining intact. With 4-hydroxyl-TEMPO esterification and with 4-amino-TEMPO amide couplings are possible starting from the free alcohol and amine moieties, respectively.…”

Section: Physical Properties and Reactivitymentioning

confidence: 99%

“…Even though Grignard compounds readily add to the carbonyl function of 4-oxo-TEMPO without interfering with the nitroxide moiety, , nitroxides can also directly react with C nucleophiles, albeit at a slower rate. Indeed, the oxidation of Grignard compounds such as phenyl or alkyl Grignard reagents or alkyllithium with TEMPO was reported.…”

Section: Oxidation Reactionsmentioning

confidence: 99%

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Organic Synthesis Using Nitroxides

Leifert

Studer

2023

Chem. Rev.

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Nitroxides, also known as nitroxyl radicals, are long-lived or stable radicals with the general structure R 1 R 2 N−O • . The spin distribution over the nitroxide N and O atoms contributes to the thermodynamic stability of these radicals. The presence of bulky N-substituents R 1 and R 2 prevents nitroxide radical dimerization, ensuring their kinetic stability. Despite their reactivity toward various transient C radicals, some nitroxides can be easily stored under air at room temperature. Furthermore, nitroxides can be oxidized to oxoammonium salts (R 1 R 2 N�O + ) or reduced to anions (R 1 R 2 N−O − ), enabling them to act as valuable oxidants or reductants depending on their oxidation state. Therefore, they exhibit interesting reactivity across all three oxidation states. Due to these fascinating properties, nitroxides find extensive applications in diverse fields such as biochemistry, medicinal chemistry, materials science, and organic synthesis. This review focuses on the versatile applications of nitroxides in organic synthesis. For their use in other important fields, we will refer to several review articles. The introductory part provides a brief overview of the history of nitroxide chemistry. Subsequently, the key methods for preparing nitroxides are discussed, followed by an examination of their structural diversity and physical properties. The main portion of this review is dedicated to oxidation reactions, wherein parent nitroxides or their corresponding oxoammonium salts serve as active species. It will be demonstrated that various functional groups (such as alcohols, amines, enolates, and alkanes among others) can be efficiently oxidized. These oxidations can be carried out using nitroxides as catalysts in combination with various stoichiometric terminal oxidants. By reducing nitroxides to their corresponding anions, they become effective reducing reagents with intriguing applications in organic synthesis. Nitroxides possess the ability to selectively react with transient radicals, making them useful for terminating radical cascade reactions by forming alkoxyamines. Depending on their structure, alkoxyamines exhibit weak C−O bonds, allowing for the thermal generation of C radicals through reversible C−O bond cleavage. Such thermally generated C radicals can participate in various radical transformations, as discussed toward the end of this review. Furthermore, the application of this strategy in natural product synthesis will be presented.

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