Cationic carbon to nitrogen rearrangements in the reactions of N-(sulfonyloxy)amines with aldehydes

Rates of thermal decomposition of title compounds have been measured using a static reaction system. They undergo a unimolecular first-order elimination to give arylnitrile and the corresponding substituted amides. The decomposition parallels that of Narylidenamino cyclic amide. The relative elimination rates at 600 K were calculated. The kinetic data reveal that the electronic effects of substituents, such as methyl, phenyl, benzyl, and allyl groups, are associated with the opposing directions in which the lone pair of electrons on the nitrogen atom of the arylidene moiety is being delocalized.

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“…1 H NMR spectroscopic data are identical to those reported in [24]. 1 H NMR spectroscopic data are identical to those reported in [25].…”

Section: P-methyl-n-methylbenzamide Lc-ms (M/z): 150 (M + 1)supporting

confidence: 78%

“…LC–MS ( m / z ): 166 (M + 1). 1 H NMR spectroscopic data are identical to those reported in 24. p‐Chloro‐N‐methylbenzamide . LC–MS ( m / z ): 170 (M + 1).…”

Section: Methodssupporting

confidence: 69%

Comparative studies on the pyrolysis of N‐arylideneaminoamides: Kinetic and mechanistic studies

Al‐Awadi

Ibrahim

Patel

et al. 2006

Int J of Chemical Kinetics

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“…A mides and nitriles are broadly important compounds for the synthesis of materials, agrochemicals, and pharmaceuticals (1,2). The Schmidt reaction is one of the most efficient nitrogenation approaches to access amides and nitriles from aldehydes and ketones with HN 3 or alkyl azides (3)(4)(5)(6)(7)(8)(9)(10)(11)(12). Discovered in 1923, it has been used extensively by synthetic chemists for almost a century.…”

mentioning

confidence: 99%

Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles

Liu

Zhang

et al. 2020

Science

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The Schmidt reaction has been an efficient and widely used synthetic approach to amides and nitriles since its discovery in 1923. However, its application often entails the use of volatile, potentially explosive, and highly toxic azide reagents. Here, we report a sequence whereby triflic anhydride and formic and acetic acids activate the bulk chemical nitromethane to serve as a nitrogen donor in place of azides in Schmidt-like reactions. This protocol further expands the substrate scope to alkynes and simple alkyl benzenes for the preparation of amides and nitriles.

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“…[22] All the epoxy alcohols are known compounds. [2,3] The hydroxamic acids in Table 2 are known compounds (5b, [37] 5c, [38] 5d, [27] 5e, [39] 5f [28] and 5g [40] ) and were synthesized according to procedures reported in the literature. [27,28] The enantiomeric excesses of the epoxy alcohols 4a and 4c were determined by 1 H NMR spectral analysis of the corresponding acetylated alcohols using Eu(hfc) 3 ; [2,3] the enantiomeric excesses of 4d, 4f, 4h and 4i were determined by 1 H NMR spectral analysis of the corresponding Mosher esters; [2,3] the enantiomeric excesses of 4b and 4e were determined by HPLC analysis on Chiralcel OD and Chiralpak AD chiral columns.…”

Section: Methodsmentioning

confidence: 99%

Vanadium‐Catalyzed Asymmetric Epoxidation of Allylic Alcohols Mediated by (+)‐Norcamphor‐Derived Hydroperoxide

2005

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A protocol for the asymmetric epoxidation of allylic alcohols has been established that employs VO(acac)2 as catalyst, the commercial achiral hydroxamic acid, N‐hydroxy‐N‐phenylbenzamide, and optically pure (+)‐norcamphor‐derived hydroperoxide as oxygen atom donor and chiral source. Variation of the reaction parameters has a significant effect on the level of asymmetric induction. Under optimized conditions, the epoxy alcohols have been isolated in good yields with up to 67 % ee and complete control of the diastereoselectivity. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Cationic carbon to nitrogen rearrangements in the reactions of N-(sulfonyloxy)amines with aldehydes

Cited by 15 publications

References 1 publication

Comparative studies on the pyrolysis of N‐arylideneaminoamides: Kinetic and mechanistic studies

Comparative studies on the pyrolysis of N‐arylideneaminoamides: Kinetic and mechanistic studies

Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles

Vanadium‐Catalyzed Asymmetric Epoxidation of Allylic Alcohols Mediated by (+)‐Norcamphor‐Derived Hydroperoxide

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