1,3-Dipolar cycloadditions of ethoxycarbonyl-nitrile benzylimine and synthesis of ß-amino acids. Synthesis and reactions of ethyl 2-chloro-2-ethoxyacetate and 2-chloro-2-ethoxyacetylchloride

K.K. Bach, H.R. El-Seedi, H.M. Jensen, H.B. Nielsen, I. Thomsen, K.B.G. Torssell

    Research output: Contribution to journalJournal articleResearchpeer-review

    Abstract

    The principles of 1,2-cyano-hydroxylation of olefins were applied to the preparation of 1,2-cyano-amines. The dipole component of this cycloaddition was nitrile imines, which formed pyrazolines with olefins. Ring cleavage was accomplished by thermolysis of 3-carboxypyrazolines, which gave 1,2-cyano-amines and subsequent hydrolysis gave beta-amino acids. The syntheses of the title reagents were described. Ethyl 2-chloro-2-ethoxy-acetate gave selectively oximes, hydrazones, nitrones, and phosphonium salts with hydroxylamine, hydrazines, N-substituted hydroxylamines and triphenylphosphine respectively. The phosphonium salt was used in a Wittig reaction with aldehydes to give alpha-ketoesters. Treatment of the acid chloride with allyl alcohols and subsequently with a monosubstituted hydroxylamine gave the allylic ester nitrone, which underwent intramolecular cyclization. Similarly, intramolecular cyclizations were carried out with the allylic ester - nitrile oxide and allylic ester - nitrile imine systems.
    Original languageEnglish
    JournalTetrahedron
    Volume50
    Issue number25
    Pages (from-to)7543-7556
    ISSN0040-4020
    DOIs
    Publication statusPublished - 1994

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