An unexpected involvement of ethyl-2-cyano-2-(hydroxyimino) acetate cleaved product in the promotion of the synthesis of nitriles from aldoximes: a mechanistic perception

Dev, Dharm; Palakurthy, Nani Babu; Kumar, Nitesh; Mandal, Bhubaneswar

doi:10.1016/j.tetlet.2013.05.149

Cited by 17 publications

(12 citation statements)

References 19 publications

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“…Furthermore, Mandal reported Oxyma sulfonate esters as efficient promotors for the conversion of aldoximes into nitriles under mild conditions. 58 The reaction mechanism proposed was through nucleophilic aldoxime attack on either the electrophilic center of sulfur (path A) or the elec-trophilic center of the carbonyl carbon (path B) of the Oxyma sulfonate esters. NMR and X-ray crystal studies of the intermediates revealed, unexpectedly, that the reaction mechanism was more favorable through the involvement of the OxymaPure-cleaved product of path B (Scheme 16).…”

Section: Scheme 15 Synthesis Of Sulfonamidesmentioning

confidence: 99%

OxymaPure Coupling Reagents: Beyond Solid-Phase Peptide Synthesis

et al. 2020

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OxymaPure [ethyl 2-cyano-2-(hydroxyimino)acetate] is an exceptional reagent with which to suppress racemization and enhance coupling efficiency during amide bond formation. The tremendous popularity of OxymaPure has led to the development of several Oxyma-based reagents. OxymaPure and its derived reagents are widely used in solid- and solution-phase peptide chemistry. This review summarizes the recent developments and applications of OxymaPure and Oxyma-based reagents in peptide chemistry, in particular in solution-phase chemistry. Moreover, the side reaction associated with OxymaPure is also discussed.1 Introduction2 Oxyma-Based Coupling Reagents2.1 Aminium/Uronium Salts of OxymaPure2.2 Phosphonium Salts of OxymaPure2.3 Oxyma-Based Phosphates2.4 Sulfonate Esters of OxymaPure2.5 Benzoate Esters of OxymaPure2.6 Carbonates of OxymaPure Derivatives3 OxymaPure Derivatives4 Other Oxime-Based Additives and Coupling Reagents5 Side Reactions Using OxymaPure Derivatives6 Conclusion7 List of Abbreviations

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Section: Scheme 15 Synthesis Of Sulfonamidesmentioning

confidence: 99%

OxymaPure Coupling Reagents: Beyond Solid-Phase Peptide Synthesis

et al. 2020

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“…It has been found that Oxyma (6) can undergo side-reactions at the ethoxylcarbonyl group. 21,24 Therefore we also studied the tert-butyl ester 8 (derived from tert-butyl cyanoacetate) 25 and the bis-nitrile 9 (derived from malonitrile) 26 (Table 1). In order to complete the series we included the bis-ethoxycarbonyl derivative 10 (derived from diethyl malonate).…”

Section: Design and Synthesis Of Oxime-based Benzoylating Reagentsmentioning

confidence: 99%

Investigation of benzoyloximes as benzoylating reagents: benzoyl-Oxyma as a selective benzoylating reagent

et al. 2016

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Hydroxybenzotriazole (HOBt) and HOBt-derived reagents have been classified as Class I explosives, with restrictions on their transportation and storage. We explored a range of benzoylated oxime-based reagents as alternatives to benzoyloxybenzotriazole (BBTZ) for the selective benzoylation of carbohydrate polyols. Benzoylated oximes derived from 2-hydroximino-malononitrile, ethyl 2-hydroximino-2-cyanoacetate (Oxyma), and tert-butyl 2-hydroximino-2-cyanoacetate were most effective for benzoylation of a simple primary alcohol, with yields approaching that obtained for BBTZ. When applied to carbohydrate diols, the most effective reagent was identified as benzoyl-Oxyma. Benzoyl-Oxyma is a highly crystalline, readily prepared alternative to BBTZ, useful in the selective benzoylation of carbohydrate polyols.

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“…We have achieved the conversion of the carboxylic acids to amides, peptides, esters, thioesters, hydroxamates, ureas, heterocyclic compounds such as benzoxazoles and benzthiazoles by using I . Conversion of aldoximes to nitriles was also possible by using I . Excellent racemization suppression capability, ease of preparation and recyclable nature, of the reagent are major advantages of this reagent.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of β‐Amino Alcohols Using Ethyl 2‐Cyano‐2‐(2‐nitrobenzenesulfonyloxyimino)acetate (o‐NosylOXY)

et al. 2018

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We describe a mild and efficient method for the direct synthesis of b-amino alcohols from N-protected amino acids using ethyl-2-cyano-2-(2-nitrophenylsulfonyloxyimino)acetate (ortho-Nosy-lOXY). The reaction sequence includes activation of carboxylic acid, followed by reduction with sodium borohydride, resulting in b-amino alcohols in good yields. This method is compatible with various N-protecting groups as well as the side chain protecting groups of amino acids. The excellent racemization suppression capability and recyclable nature of ortho-NosylOXY is an added feature to the in-situ activation mediated carboxylic acid reduction.

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An unexpected involvement of ethyl-2-cyano-2-(hydroxyimino) acetate cleaved product in the promotion of the synthesis of nitriles from aldoximes: a mechanistic perception

Cited by 17 publications

References 19 publications

OxymaPure Coupling Reagents: Beyond Solid-Phase Peptide Synthesis

OxymaPure Coupling Reagents: Beyond Solid-Phase Peptide Synthesis

Investigation of benzoyloximes as benzoylating reagents: benzoyl-Oxyma as a selective benzoylating reagent

Synthesis of β‐Amino Alcohols Using Ethyl 2‐Cyano‐2‐(2‐nitrobenzenesulfonyloxyimino)acetate (o‐NosylOXY)

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