Direct synthesis of secondary amides from ketones through Beckmann rearrangement using O-(mesitylsulfonyl)hydroxylamine

Chandra, Dinesh; Verma, Saumya; Pandey, Chandra Bhan; Yadav, Ajay; Kumar, Puneet; Tiwari, Bhoopendra; Jat, Jawahar L.

doi:10.1016/j.tetlet.2020.151822

Cited by 11 publications

(6 citation statements)

References 30 publications

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“…Procedure A; purification with dichloromethane/ethyl acetate 20:1 as the eluent; yellow oil (85 mg, 74% yield). Analytical data were in good accordance with reported data …”

Section: Methodssupporting

confidence: 89%

Polyphosphoric Acid Esters Promoted Synthesis of Quinazolin-4(3H)-imines from 2-Aminobenzonitrile

et al. 2023

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A novel method for the synthesis of quinazolin-4(3H)-imines (QIs) by trimethylsilyl polyphosphate (PPSE) promoted reaction of 2-aminobenzonitrile with secondary amides is reported. The reaction is general and allows for the synthesis of N 3 -aryl and N 3 -alkyl QIs with variable 2-substituents affording high yields. The procedure was extended to derivatives bearing additional functional groups. The method is operationally simple, involves easily available starting materials and a mild dehydrating agent, with wide functional group tolerance. The reaction procedure proved to be suitable for scaling-up. A possible reaction path via an intermediate nitrilium ion is proposed on the basis of literature data and experimental observations.

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“…Procedure A; purification with dichloromethane/ethyl acetate 20:1 as the eluent; yellow oil (85 mg, 74% yield). Analytical data were in good accordance with reported data …”

Section: Methodssupporting

confidence: 89%

Polyphosphoric Acid Esters Promoted Synthesis of Quinazolin-4(3H)-imines from 2-Aminobenzonitrile

et al. 2023

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“…Chandra et al [134] recently described a direct method for producing amides from ketones by using o-(Mesitylsulfonyl) hydroxylamine (MSH). Studying the range of substrates for this MSH-mediated Beckmann rearrangement, para-substituted acetophenones with both electron-donating (Me, OH, OMe) and electron-withdrawing (Br, Cl, F) groups were used.…”

Section: Using O-(mesitylsulfonyl) Hydroxylamine (Msh)mentioning

confidence: 99%

Comprehensive updates on Beckmann Rearrangement

Kaushik,

Jain,

Malik

et al. 2024

ChemistrySelect

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Beckmann rearrangement has been quite successful in the preparation of many medicinally potent scaffolds. In synthetic organic chemistry, the Beckmann rearrangement is quite popular, caprolactam is synthesized from cyclohexanone oxime on a large scale for Nylon‐6 production. The function of numerous catalysts and media in the Beckmann rearrangement has been discussed in depth in this review. In the last 20 years, Beckmann rearrangement catalysis has evolved from a potentially hazardous to a more environmentally friendly catalyst, as a result of greater usage. Catalytic performance and synthetic performance of various catalytic systems have been re‐evaluated in the present review article.

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“…In view of the limits and potential problems of existing methods, development of a simple method for the direct access of primary amines from aryl boronic acid is meaningful to enrich the synthetic chemist‘s toolbox. In continuation of our ongoing work on O ‐substituted hydroxylamine derivatives to develop efficient and simple methodologies, [7a–c] we were next interested to develop an efficient, one‐pot, mild, and transition‐metal‐free method using bench stable N ‐Boc‐ O ‐tosylhydroxylamine (TsONHBoc) as a nitrogen donor for conversion of aryl boronic acids/derivatives to primary aromatic amines. Recently, Hashmi and the group used this reagent for a metal‐free arene C−H amination [7d] .…”

Section: Introductionmentioning

confidence: 99%

Metal‐Free Direct Transformation of Aryl Boronic Acid to Primary Amines

et al. 2022

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In this work, we report a transition-metal free approach for the construction of primary aromatic amines from aryl boronic acids and esters with N-Boc-O-tosylhydroxylamine as an amine surrogate. Bench stable TsONHBoc is easy to use and it produces a non-interfering water-soluble by-product. The protocol is operative for both electron-rich and electron-deficient aryl boronic acids under acidic conditions, where the former arenes affords a better yield of the desired product. Even, sterically hindered and halogenated substrates are easily amenable under this reaction condition. The current protocol can be scaled up to produce gram-scale primary aromatic amines.

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Direct synthesis of secondary amides from ketones through Beckmann rearrangement using O-(mesitylsulfonyl)hydroxylamine

Cited by 11 publications

References 30 publications

Polyphosphoric Acid Esters Promoted Synthesis of Quinazolin-4(3H)-imines from 2-Aminobenzonitrile

Polyphosphoric Acid Esters Promoted Synthesis of Quinazolin-4(3H)-imines from 2-Aminobenzonitrile

Comprehensive updates on Beckmann Rearrangement

Metal‐Free Direct Transformation of Aryl Boronic Acid to Primary Amines

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