• Title/Summary/Keyword: Acyl transfer reaction

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A Mechanistic Study on Acyl Transfer Reactions of Aryl Substituted Benzoates Between Aryloxides

  • Ik-Hwan Um;Jae-Shin Jeon;Dong-Sook Kwon
    • Bulletin of the Korean Chemical Society
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    • v.12 no.4
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    • pp.406-410
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    • 1991

  • Second order rate constants have been measured spectrophotometrically for reactions of 4-nitrophenyl substituted benzoates with various aryloxides and aryl benzoates with p-chlorophenoxide. The reactivity has exhibited significant dependences on the electronic nature of the substituent in the acyl moiety of the substrate and in the nucleophilic phenoxide, while the substituent in the leaving phenoxide has little influenced the reactivity. The Bronsted coefficient $\beta$ values so obtiained support that the present acyl transfer reaction proceeds via a stepwise mechanism in which the nucleophilic attack would be the rate-determining step. Interestingly, the magnitude of the $\betaacyl$ and $\beta$ nuc increases with increasing reactivity, implying that the reactivity selectivity principle is not operative in the present system. The failure of the reactivity selectivity principle is attributed to a change in transition state structure upon the substituent variation in the present acyl transfer reaction.

  • https://doi.org/10.5012/bkcs.1991.12.4.406 인용 PDF

Synthesis of Dienamides via the Reaction of Nitrile with Allylindium Reagents and Intramolecular Acyl Group Quenching Cascade

  • Kim, Sung-Hwan;Kim, Yu-Mi;Kim, Jae-Nyoung
    • Bulletin of the Korean Chemical Society
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    • v.31 no.8
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    • pp.2351-2356
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    • 2010

  • Various dienamide derivatives were synthesized in reasonable yields from benzonitriles having an amide moiety at the ortho-position, via the sequential (i) In-mediated allylation of nitrile moiety to form an imine intermediate, (ii) intramolecular quenching of an acyl group by the imine intermediate, and (iii) a proton transfer to dienamide.

  • https://doi.org/10.5012/bkcs.2010.31.8.2351 인용 PDF KSCI