nBu<sub>4</sub>NI-catalyzed intermolecular C–O cross-coupling reactions: synthesis of alkyloxyamines

Lv, Yunhe; Sun, Kai; Wang, Tingting; Li, Gang; Pu, Weiya; Chai, Nannan; Shen, Hui‐Hui; Wu, Yingtao

doi:10.1039/c5ra12691f

Cited by 39 publications

(5 citation statements)

References 64 publications

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“… , A disadvantage of this method is that the arene or alkene substrate needs to be added in a large excess (10 equiv). The same transformation was also realized using cerium(IV) ammonium nitrate (CAN) or tert -butylhydroperoxide (TBHP) and tetrabutylammonium iodide (TBAI) − or other (transition) metals as co-oxidants. Of note, with TBHP/TBAI, tert -butoxyl radicals are generated, which can also engage in benzylic C–H abstraction .…”

Section: Oxidation Reactionsmentioning

confidence: 99%

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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Section: Oxidation Reactionsmentioning

confidence: 99%

Organic Synthesis Using Nitroxides

Leifert

Studer

2023

Chem. Rev.

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“…The reaction of ethyl acetoacetate 43 with benzylamine 44 in the presence of n-Bu4NI catalyst (20 mol%), and an oxidant (4.0 equiv.) to have the product 45 with good yield as explained in table 4 The mechanism of the cascade reaction [120] was explained by Ishihara and co-workers, [121] suggested that the active iodine species ammonium hypoiodite ( The aerobic C-H oxidation of C(sp3)-H activation by organocatalytic (metal free) recyclable catalyst TEMPO. TEMPO one of the most choice in industry [122] and has been widely used for the oxidation of alcohols to carbonyls, [123,124], and it use in the oxidative functionalization of other functionalities represents an important challenge and the examples are very limited [125][126][127][128][129][130][131].…”

Section: C-h Bond Oxidationmentioning

confidence: 99%

Review for metal and organocatalysis of heterocyclic C-H functionalization

El‐Sayed¹,

Khaireldin²,

Elhefny³

2021

World J. Adv. Res. Rev.

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Over the last few decades, signiﬁcant efforts have been put forth towards the C−H bond group functionalization by transition-metalcatalysis and organocatalysis. Several efficient strategies to convert C-H bond to other groups C-C, C-N, C-O bonds have been implemented. The most attractive C-H bond functionalization was the C-H heterocyclic compounds activation that is practical method in organic synthesis. The new C–C, C–N and C–O bond as formed from the C-H bond activation by two diverse ways metal catalysis and/or organocatalysis. The most important is the synthesis of new bioactive heterocyclic compounds by easy and less expensive materials. In this review, we will cover most of the syntheses of heterocyclic derivatives by the functionalization of C-H bond in metal and organocatalytic reagents.

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“…Precursor 2 and R 1 ONH 2 were synthesized as literature report. [18][19][20] All of the yields were not optimized.…”

Section: Instruments and Materialsmentioning

confidence: 99%

Design, synthesis, and insecticidal activity of novel 1-alkoxy-2-nitroguanidines

et al. 2018

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nBu₄NI-catalyzed intermolecular C–O cross-coupling reactions: synthesis of alkyloxyamines

Abstract: nBu4NI-catalyzed cross-coupling of benzyl and allylic compounds with N-hydroxyphthalimide for the synthesis of alkyloxyamines were realized for the first time.

Cited by 39 publications

References 64 publications

Organic Synthesis Using Nitroxides

Organic Synthesis Using Nitroxides

Review for metal and organocatalysis of heterocyclic C-H functionalization

Design, synthesis, and insecticidal activity of novel 1-alkoxy-2-nitroguanidines

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nBu4NI-catalyzed intermolecular C–O cross-coupling reactions: synthesis of alkyloxyamines

Abstract: nBu4NI-catalyzed cross-coupling of benzyl and allylic compounds with N-hydroxyphthalimide for the synthesis of alkyloxyamines were realized for the first time.

Cited by 39 publications

References 64 publications

Organic Synthesis Using Nitroxides

Organic Synthesis Using Nitroxides

Review for metal and organocatalysis of heterocyclic C-H functionalization

Design, synthesis, and insecticidal activity of novel 1-alkoxy-2-nitroguanidines

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Product

Resources

About

nBu₄NI-catalyzed intermolecular C–O cross-coupling reactions: synthesis of alkyloxyamines