Copper‐Catalyzed Mild Nitration of Protected Anilines

Hernando, Elier; Castillo, Rafael R.; Rodríguez, Nuria; Arrayás, Ramón Goméz; Carretero, Juan C.

doi:10.1002/chem.201404000

Cited by 46 publications

(31 citation statements)

References 57 publications

(45 reference statements)

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“…On the basis of above experimental evidence and related literature, [12,[19][20][21][22] the plausible reaction mechanisms of these nitration processes are proposed in Scheme 5. First, TBN undergoes a thermal homolysis to liberate the alkoxyl and nitric oxide radicals.…”

Section: Resultsmentioning

confidence: 98%

“…[20] In the arene nitration process, it is assumed that the initial one-electron oxidation of the anilide by copper(II) results in the formation of anilide radical A. [22] In the olefin nitration process, according to Jiao's work, [20c] NO 2 · attacks the alkenyl unit followed by an anti elimination [12] in the presence of another nitro radical to yield the nitro-substituted olefin stereoselectively. [22] In the olefin nitration process, according to Jiao's work, [20c] NO 2 · attacks the alkenyl unit followed by an anti elimination [12] in the presence of another nitro radical to yield the nitro-substituted olefin stereoselectively.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Effective Nitration of Anilides and Acrylamides by tert‐Butyl Nitrite

Yan

Jiang

2015

Eur J Org Chem

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Nitro compounds are important intermediates in synthetic organic chemistry and the chemical industry. Herein, the efficient copper-catalyzed [10 % Cu(NO 3 ) 2 ·3H 2 O] nitration of anilides was developed by using TBN (tert-butyl nitrite) as a nitrating reagent to give the corresponding nitro-substituted aromatic products in good to excellent yields. The use of TBN also led to the selective nitration of acrylamides at room temperature to afford only the (E) isomer of the nitration product.[a] State Key A series of anilides and acrylamides with a broad array of functional groups were well-tolerated by this procedure. This synthetic method has many advantages, which include inexpensive starting materials, mild reaction conditions, a fast reaction rate, and high yields. A mechanistic investigation indicates that a nitro radical, which is generated from the thermal homolysis of TBN, is involved in the two nitration processes.www.eurjoc.org

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Effective Nitration of Anilides and Acrylamides by tert‐Butyl Nitrite

Yan

Jiang

2015

Eur J Org Chem

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“…N ‐(4‐methyl‐2‐nitrophenyl)benzamide (2r): The general procedure was followed by using N ‐( p ‐tolyl)benzamide (0.5 mmol, 105 mg), NaNO 2 (69 mg, 0.5 mmol), K 2 S 2 O 8 (270 mg, 1.0 mmol), and AgNO 2 (8 mg, 10 mol‐%). Purification by column chromatography (silica gel; n ‐hexane/EtOAc, 2:1) gave product 2r (113 mg, 89 %) as a yellow solid, m.p.…”

Section: Methodsmentioning

confidence: 99%

“…An efficient Fe(NO 3 ) 3 · 9H 2 O promoted ortho ‐nitration of aniline derivatives has been developed by Huo in 2018 [Scheme , Equation (3)] . Copper‐catalyzed nitration of protected anilines with HNO 3 was reported by Carretero in 2014 [Scheme , Equation (4)] . Yan et al used a combination of tert ‐butyl nitrite (TBN) and a catalytic amount of Cu(NO 3 ) 2 · 3H 2 O for the efficient aryl nitration of aromatic amides [Scheme , Equation (5)] .…”

Section: Introductionmentioning

confidence: 99%

Silver‐Catalyzed Chemo‐ and Regioselective Nitration of Anilides

Kianmehr

Nasab

2018

Eur J Org Chem

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A new and efficient Ag‐catalyzed method for the nitration of anilides by using sodium nitrite as a cheap and available NO2 source has been developed. This C–H functionalization reaction is ortho‐selective, achieves moderate to high yields and shows excellent functional group tolerance. Furthermore, it provides a novel approach to ortho‐nitrated anilides, which are very tricky to access with traditional methods.

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“…Although in some cases, a mild nitration agent such as tertbutyl nitrite (TBN) was used, the reaction required an elevated temperature [146][147][148][149][150]. As can be seen in Figure 17, the reaction is initiate with the excitation of the photocatalyst, which Aryl C-H amination of ortho positions: synthesis of carbazoles…”

Section: C-h Nitration Of Protected Anilinesmentioning

confidence: 99%

Recent developments in photoredox-catalyzed remote ortho and para C–H bond functionalizations

Siddiqui¹,

Ali²

2020

Beilstein J. Org. Chem.

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In recent years, the research area of direct C–H bond functionalizations was growing exponentially not only due to the ubiquity of inert C–H bonds in diverse organic compounds, including bioactive natural and nonnatural products, but also due to its impact on the discovery of pharmaceutical candidates and the total synthesis of intricate natural products. On the other hand, more recently, the field of photoredox catalysis has become an indispensable and unparalleled research topic in modern synthetic organic chemistry for the constructions of challenging bonds, having the foremost scope in academia, pharmacy, and industry. Therefore, the development of green, simpler, and effective methodologies to accomplish direct C–H bond functionalization is well overdue and highly desirable to the scientific community. In this review, we mainly highlight the impact on, and the utility of, photoredox catalysts in inert ortho and para C–H bond functionalizations. Although a surge of research papers, including reviews, demonstrating C–H functionalizations have been published in this vital area of research, to our best knowledge, this is the first review that focuses on ortho and para C–H functionalizations by photoredox catalysis to provide atom- and step-economic organic transformations. We are certain that this review will act as a promoter to highlight the application of photoredox catalysts for the functionalization of inert bonds in the domain of synthetic organic chemistry.

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Copper‐Catalyzed Mild Nitration of Protected Anilines

Cited by 46 publications

References 57 publications

Effective Nitration of Anilides and Acrylamides by tert‐Butyl Nitrite

Effective Nitration of Anilides and Acrylamides by tert‐Butyl Nitrite

Silver‐Catalyzed Chemo‐ and Regioselective Nitration of Anilides

Recent developments in photoredox-catalyzed remote ortho and para C–H bond functionalizations

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