Recent Advances in Radical Nitration Using tert-Butyl Nitrite

Song, Shuwei; Dong, Youren; Ge, Guo‐Ping; Li, Qiang; Wei, Wanzhi

doi:10.1055/s-0039-1690789

Cited by 28 publications

(16 citation statements)

References 27 publications

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“…Featuring high reactivity over a wide range of miscible substrates, these on‐water systems outperformed the reported homogeneous system [12c] . Impressively, the reactivity of substituted phenols such as 4‐halogenophenols was not reduced despite the decreased O−H bond dissociation free energies, which contrasts with the homogeneous systems using tert ‐butyl nitrite [12b,17] . Although raspberry ketone ( 1 l ) may undergo α‐oximation upon reaction with isopropyl nitrite as a NO + source, [18] the optimal conditions allowed exclusive nitration of the phenol moiety.…”

Section: Resultsmentioning

confidence: 96%

2‐Methoxyethyl Nitrite as a Reagent for Chemoselective On‐Water Nitration

Kitanosono

Hashidoko

Yamashita

et al. 2022

Chemistry An Asian Journal

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An on-water approach has been developed that allows a nitration of tyrosines and phenols under mild conditions. We envisioned that the assembly of tyrosine/ tyrosyl radical couples with interfacial water molecules would realize a biomimetic stacking hydrogen atom transfer (HAT) transition state to facilitate the electron-transfer process. The optimal organic nitrite, 2-methoxyethyl nitrite, resulted in rapid coupling of the tyrosyl radicals with * NO 2 at the oilwater interface to afford the nitrated phenols. Many characteristics found in our on-water strategy are distinct from other complementary systems that include radical nitration. These enticing roles of water in the reaction process introduce new avenues to explore in the design of synthetic organic chemistry systems.

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Section: Resultsmentioning

confidence: 96%

2‐Methoxyethyl Nitrite as a Reagent for Chemoselective On‐Water Nitration

Kitanosono

Hashidoko

Yamashita

et al. 2022

Chemistry An Asian Journal

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“…It is a versatile reagent and the least toxic among other alkyl nitrites. 32 TBN is a yellow, highly flammable, and toxic liquid with great solubility in most organic solvents and it is commercially available (~100 mL/$50). TBN-mediated transformations commonly proceed via radical pathways initiated by thermal or aerobic conditions, as well as irradiation.…”

Section: Alkyl Nitritesmentioning

confidence: 99%

Organic Nitrating Reagents

Patra¹,

Mosiagin²,

Katayev³

et al. 2022

Synthesis

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Nitro compounds are vital raw chemicals that are widely used in academic laboratories and industries for the preparation of various drugs, agrochemicals, and materials. Thus, nitrating reactions are of great importance for chemists and are even taught in schools as one of the fundamental transformations in organic synthesis. Since the discovery of the first nitrating reactions in the 19th century, progress in this field has been constant. Yet, for many years the classical electrophilic nitration approach using a mixture of strong mineral acids dominated the field. However, in recent decades, the attention of researchers has focused on new reactivity and new reagents that can provide access to nitro compounds in a practical and straightforward way under mild reaction conditions. Organic nitrating reagents have played a special role in this field since they have enhanced reactivity. They also allow nitration to be carried out in an ecofriendly and sustainable manner. This review examines the development and application of organic nitrating reagents.1 Introduction2 Organic Nitrating Reagents2.1 Alkyl Nitrites2.2 Nitroalkanes2.3 Alkyl Nitrates2.4 N-Nitroamides2.5 N-Nitropyrazole2.6 N-Nitropyridinium Salts3 Organic Nitrating Reagents Generated In Situ3.1 Acyl Nitrates3.2 Trimethylsilyl Nitrate3.3 Nitro Onium Salts4 Organic Nitronium Salts5 Organic Nitrates and Nitrites5.1 Ammonium Nitrates5.2 Heteroarylium Nitrates5.3 Other Organic Nitrates5.4 Organic Nitrites6 Conclusion and Outlook

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“…To avoid this, a nonmetallic reagent which is safe and easily storable and which can generate a NO radical was much needed. [38] Therefore, a new reagent system consisting of tertbutyl nitrite ( t BuONO) and TEMPO was developed for the nitration of olefins under aerobic conditions (Scheme 9). [39] This protocol demonstrated a similar excellent functional group tolerance as a wide array of aromatic, aliphatic and heteroaromatic olefins were successfully nitrated in excellent yields.…”

Section: Earlier Reports and Our Contributionmentioning

confidence: 99%

“…To avoid this, a nonmetallic reagent which is safe and easily storable and which can generate a NO radical was much needed [38] . Therefore, a new reagent system consisting of tert ‐butyl nitrite ( t BuONO) and TEMPO was developed for the nitration of olefins under aerobic conditions (Scheme 9).…”

Section: Direct Nitration Of Olefinsmentioning

confidence: 99%

Recent Advances in the Nitration of Olefins

Paul

Maity

Panja

2021

The Chemical Record

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Nitroolefins are important synthetic intermediates in the field of organic synthesis as well as in medicinal chemistry. The high reactivity of nitroalkenes due to the polarized double bond which enables them to act as Michael acceptor in conjugate addition reactions, or as a dienophile in cycloaddition makes it an essential synthetic handle for accessing complex molecules. The classical method to prepare nitroolefins is indeed the Henry nitroaldol reaction, where a carbonyl compound and nitroalkane are condensed in presence of base. Direct nitration of olefin, on the other hand, serves as a useful alternative as olefins are abundant, have broad commercial availability and easy to manipulate. In this context, numerous methods have been developed over the last few decades, focusing on direct nitration of styrene and aliphatic olefins. Furthermore, thorough literature search revealed that implementation of this class of reactions are gaining momentum as a preferred pathway to access nitroolefins, despite the presence of a powerful technique such as Henry reaction. In this review, we aim to cover recent advances in direct olefin nitration and their importance in accessing biorelevant molecules, total synthesis targets and future outlook in this specific research area.

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Recent Advances in Radical Nitration Using tert-Butyl Nitrite

Cited by 28 publications

References 27 publications

2‐Methoxyethyl Nitrite as a Reagent for Chemoselective On‐Water Nitration

2‐Methoxyethyl Nitrite as a Reagent for Chemoselective On‐Water Nitration

Organic Nitrating Reagents

Recent Advances in the Nitration of Olefins

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