Convenient and mild synthesis of nitroarenes by metal-free nitration of arylboronic acids

Wu, Xiao‐Feng; Schranck, Johannes; Neumann, Helfried; Beller, Matthias

doi:10.1039/c1cc15484b

Cited by 104 publications

(39 citation statements)

References 16 publications

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“…Based on previous literature precedents a plausible mechanism has been proposed. Initially, nitrosoarenes were formed via inter‐ or intra‐molecular activation of phenylboronic acids ( 71 ) by TBN which on further oxidation produced the desired nitroarenes ( 72 ) (Scheme ) …”

Section: Outlines Of the Reactions Involving Tbnmentioning

confidence: 99%

tert‐Butyl Nitrite (TBN), a Multitasking Reagent in Organic Synthesis

Dahiya

Sahoo

Alam

et al. 2019

Chemistry An Asian Journal

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The upsurge interesti nt he development of efficient methodologies for the constructiono fn itrogen-containing frameworks via the use of expedient reagents have been creating ar enaissance in contemporary organic chemistry.I nt his perspective, tertbutyl nitrite (TBN) is an emerging building block. Due to its uniques tructuralf eatures, it shows differential reactivity under different reaction conditions. These diverse reactivities have resulted in the construction of ad iverse array of complex N-containing molecules. The primary objective of the presentr eview is to bring the latest findings of TBN in terms of its applications in reactions (oxidation, diazotization, nitrosation, nitration, oximation, N-synthon, and miscellaneous reactions) into the limelight.F or simplicity and brevity,r eactions in each section are explained with the mechanism of formation and selected examples are given.Scheme1.Differential reactivity of TBN. 4455 MinireviewScheme4.Visible-light-promoted synthesis of selenide ethers.Scheme5.Proposed mechanism for visible-light-promoted synthesis of selenide ethers.Scheme6.TBN-mediated synthesis of selenide ethers.Scheme7.Metal-free synthesis of 4-carbonylquinolines.Scheme8.Proposed mechanism for synthesis of 4-carbonylquinolines.Scheme9.TBN-mediated demethylative borylation of methylarenes.Scheme10. Plausible mechanism for demethylative borylation of methylarenes.Scheme11. Trifluoromethylation of various aromatic amine substrates.Scheme12. Copper-catalyzed isoperfluoropropylation of anilines.Scheme13. Plausible mechanism for Cu-catalyzed isoperfluoropropylation of anilines.Scheme14. TBN-mediateddiazotizative allylation of aromatic amines.Scheme15. Oxidativecyanomethylationo fa lkenes via CÀHb ond activation.Scheme16. TBN-mediatedand Cu-catalyzedsynthesis of thioether.

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Section: Outlines Of the Reactions Involving Tbnmentioning

confidence: 99%

tert‐Butyl Nitrite (TBN), a Multitasking Reagent in Organic Synthesis

Dahiya

Sahoo

Alam

et al. 2019

Chemistry An Asian Journal

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“…, tert -butyl nitrite, was recently described by Wu, Beller and co-workers. [33] Both electron-rich and deficient substrates were well tolerated, furnishing the corresponding nitroarenes in moderate to good yields (Scheme 19). Regarding the mechanism, it was suggested reaction of the phenylboronic acids with the nitriting agent initially resulted in nitrosobenzenes, which were concomitantly oxidized in situ by air to nitrobenzenes.…”

Section: Carbon-nitrogen Bond Formationmentioning

confidence: 99%

Transition Metal‐Free ipso‐Functionalization of Arylboronic Acids and Derivatives

Zhu

Falck

2014

Adv Synth Catal

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Arylboronic acids and their derivatives have been widely exploited as important synthetic precursors in organic synthesis, materials science, and pharmaceutical development. In addition to numerous applications in transition-metal-mediated cross-coupling reactions, transition-metal-free transformations involving arylboronic acids and derivatives have recently received a surge of attention for converting the C-B bond to C-C, C-N, C-O, and many other C-X bonds. Consequently, a wide range of useful compounds, e.g., phenols, anilines, nitroarenes, and haloarenes, have been readily synthesized. Amongst these efforts, many versatile reagents have been developed and a lot of practical approaches demonstrated. The research in this promising field is summarized in the current review and organized on the basis of the type of bonds being formed.

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“…13 Indeed, a thorough literature search revealed only a handful of recent methods that can convert the C(sp 2 )-B bond of arylboronic acids and derivatives to the corresponding C(sp 2 )-N bond in the absence of transition metals. 14 For instance, boronic acids can be exchanged for highly electron-deficient nitrogen functional groups (i.e., nitro and nitroso groups) via an aromatic ipso substitution mechanism. 14a,14d,14f There were also two reports in which electrophilic aminating agents (e.g., organic azides and N,N -dialkyl -O -benzoyl hydroxylamines) reacted with arylboronic acids 14b and arylboroxines, 14g respectively, albeit under very harsh reaction conditions (>130 °C), to afford the corresponding N -monosubstituted as well as N,N -disubstituted anilines.…”

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confidence: 99%

“…14 For instance, boronic acids can be exchanged for highly electron-deficient nitrogen functional groups (i.e., nitro and nitroso groups) via an aromatic ipso substitution mechanism. 14a,14d,14f There were also two reports in which electrophilic aminating agents (e.g., organic azides and N,N -dialkyl -O -benzoyl hydroxylamines) reacted with arylboronic acids 14b and arylboroxines, 14g respectively, albeit under very harsh reaction conditions (>130 °C), to afford the corresponding N -monosubstituted as well as N,N -disubstituted anilines. Finally, excess lithiated methoxyamine (3 equiv) was found to aminate aryl pinacol boronates, although the scope of this transformation is mostly limited to electron rich substrates and base-sensitive functional groups are apparently not compatible with the reaction conditions.…”

mentioning

confidence: 99%

“…Finally, excess lithiated methoxyamine (3 equiv) was found to aminate aryl pinacol boronates, although the scope of this transformation is mostly limited to electron rich substrates and base-sensitive functional groups are apparently not compatible with the reaction conditions. 14e Herein, we disclose a metal-free, mild, operationally simple and practical approach to access primary arylamines by the direct amination of arylboronic acids (Scheme 1, II ).…”

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confidence: 99%

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Elusive Metal-Free Primary Amination of Arylboronic Acids: Synthetic Studies and Mechanism by Density Functional Theory

et al. 2012

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Herein, we disclose the first metal-free synthesis of primary aromatic amines from arylboronic acids, a reaction that has eluded synthetic chemists for decades. This remarkable transformation affords structurally diverse primary arylamines in good chemical yields, including a variety of halogenated primary anilines that often cannot be prepared via transition metal-catalyzed amination. The reaction is operationally simple, requires only a slight excess of aminating agent, proceeds under neutral or basic conditions and, importantly, it can be scaled up to provide multigram quantities of primary anilines. Density functional calculations reveal that the most likely mechanism involves a facile 1,2-aryl migration and that the presence of an ortho nitro group in the aminating agent plays a critical role in lowering the free energy barrier of the 1,2-aryl migration step.

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Convenient and mild synthesis of nitroarenes by metal-free nitration of arylboronic acids

Abstract: A novel methodology for the direct nitration of arylboronic acids has been developed. By using inexpensive tert-butyl nitrite various aromatic nitro compounds are produced in moderate to good yields (45-87%) without the need of any catalyst.

Cited by 104 publications

References 16 publications

tert‐Butyl Nitrite (TBN), a Multitasking Reagent in Organic Synthesis

tert‐Butyl Nitrite (TBN), a Multitasking Reagent in Organic Synthesis

Transition Metal‐Free ipso‐Functionalization of Arylboronic Acids and Derivatives

Elusive Metal-Free Primary Amination of Arylboronic Acids: Synthetic Studies and Mechanism by Density Functional Theory

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