Chemoselective nitration of aromatic sulfonamides with tert-butyl nitrite

Kilpatrick, Brenden; Heller, Markus; Arns, Steve

doi:10.1039/c2cc37481a

Cited by 127 publications

(52 citation statements)

References 12 publications

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“…These experiments demonstrate that the two processes may proceed by radical mechanisms with the existence of a nitro radical. N-substitution may prevent the formation of an anilide radical intermediate (according to Arn's mechanism [18] ) upon the one-electron oxidation by the Cu II species. N-substitution may prevent the formation of an anilide radical intermediate (according to Arn's mechanism [18] ) upon the one-electron oxidation by the Cu II species.…”

Section: Resultsmentioning

confidence: 99%

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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: 99%

“…[14] However, there are much fewer reports of the selective nitration of anilides [15] and acrylamides. [18] However, the nitration of aromatic amides did not occur under the same conditions (Scheme 1). It has been shown that TBN is an effective chemoselective nitrating reagent for phenols.…”

Section: Introductionmentioning

confidence: 99%

Effective Nitration of Anilides and Acrylamides by tert‐Butyl Nitrite

Yan

Jiang

2015

Eur J Org Chem

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“…In a recent publication, Koley et al reported a nitration method using TBN under acid‐free conditions, compatible with tyrosine‐containing peptides on solid support in the synthesis of fluorogenic substrates for characterization of proteases. Kilpatrick and Arns demonstrated TBN as an effective reagent for the selective nitration of aryl sulfonamides . Encouraged by the features reported in this paper, we have recently reported the nitro‐decarboxylation of α,β‐unsaturated acids for the synthesis of β‐nitrostyrenes under acid‐free conditions by TBN and extended the methodology for nitration of aromatic compounds.…”

Section: Introductionmentioning

confidence: 76%

Tertiary Butyl Nitrite Triggered Nitration of Phenols: Solvent‐ and Structure‐Dependent Kinetic Study

Kumar

Rajanna

Venkateswarlu

et al. 2016

Int J of Chemical Kinetics

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Nitration of phenols with tertiary butyl nitrite (TBN) obeyed second-order kinetics with a first-order dependence on [TBN] and [phenol] under acid-free conditions. Reaction rates were significantly altered by a change in the dielectric constant and other physical properties of solvent. The rate of nitration increased with an increase in temperature (303-323 K) in different solvent media (acetonitrile, dichloroethane, CCl 4 , dimethyl formamide (DMF), and toluene). The rates of nitration (log k) could not fit into either Amis or Kirkwood plots [log k' vs. (1/D) or [(D -1)/(2D + 1)], but the trends were better explained by the basic form of multivariate linear solvent energy relationships (MLSER) suggested by the Koppel and Palm approach on the one hand and the Kamlet and Taft approach on the other hand. These observations probably substantiate that cumulative contributions of basic solvent parameters (equilibrium as well as frictional solvent effects) and solvent-solute interactions for solvation of transition state during nitration of phenols. Reaction rates accelerated with the introduction of electrondonating groups and retarded with electron-withdrawing groups. Accordingly, the reactivity of structurally different phenols was found to follow the following sequence:

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“…32 The tosyl protected amine tetralone 7d was obtained in 96% yield in pyridine with tosyl chloride (p-TsCl) (entry 2). 33 In a similar manner, base labile Fmoc protected amine 7e was formed in 98% yield with 9-fluorenylmethyloxycarbonyl chloride (Fmoc-Cl) and pyridine in DCM (entry 3). 34 The acetylation of tetralone 6 was achieved using 4-dimethylaminopyridine (DMAP), acetic anhydride (Ac 2 O) in Et 3 N giving acetyl protected ketone 7f in 97% yield (entry 4).…”

Section: Resultsmentioning

confidence: 98%

Iodine(III)-Mediated Ring Contraction Reactions: Synthesis of Oxygen- and Nitrogen-Substituted Indanes

Ahmad¹,

Júnior²

2016

Journal of the Brazilian Chemical Society

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The synthesis of oxygen-and nitrogen-substituted indanes was successfully performed by iodine(III)-mediated ring contraction of 1,2-dihydronaphthalenes. Acetoxy and benzoyloxy alkenes afforded indanes in 60-71% yield, irrespective of their position on aromatic ring. Similarly, the nitrogen containing substrates protected with 9-fluorenylmethyloxycarbonyl (Fmoc) and benzoyl (Bz) groups smoothly undergoes ring contraction giving indanes in 64-77% yield. The tosyl-protected substrate resulted only in addition products.

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Chemoselective nitration of aromatic sulfonamides with tert-butyl nitrite

Cited by 127 publications

References 12 publications

Effective Nitration of Anilides and Acrylamides by tert‐Butyl Nitrite

Effective Nitration of Anilides and Acrylamides by tert‐Butyl Nitrite

Tertiary Butyl Nitrite Triggered Nitration of Phenols: Solvent‐ and Structure‐Dependent Kinetic Study

Iodine(III)-Mediated Ring Contraction Reactions: Synthesis of Oxygen- and Nitrogen-Substituted Indanes

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