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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 13 (1974), S. 789-804 
    ISSN: 0570-0833
    Keywords: Isocyanides ; Synthetic methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: α-Alkali-metalated isocyanides, which can be obtained from isocyanides and bases, can be used for nucleophilic introduction of (masked) α-aminoalkyl groups. Intramolecular ring-closure may then follow if a nucleophile combines at the electron sextet of the isocyanide carbon. Treatment of α-alkali-metalated isocyanides with electrophilic agents permits rapid and efficient synthesis of, inter alia, 2- and 3-amino alcohols, straight-chain, branched, and β-functional α-amino acids, olefins, vinyl isocyanides, and of a large number of mainly five-, but also six- and seven-membered aza-, diaza-, oxa-aza-, and thia-aza heterocycles.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0570-0833
    Keywords: Homoaldol reaction ; Stereoselectivity ; Synthetic methods ; Regioselectivity ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Even today, there are conspicuous gaps in the register of organic synthetic methods. Thus, numerous types of homoenolate reagents are listed; yet no generally applicable method for the homologue of the aldol addition, viz. the homoaldol addition, is to be found. The methods documented up to 1980 offer only singular solutions, and, moreover, are not stereoselective. The present article gives an overview of the existing possibilities and then describes how the gap can be closed by using a new class of homoenolate reagents: 2-alkenyl esters of N,N-diisopropylcarbamic acid are lithiated and the resulting allyllithium compounds tailored to high regio- and diastereoselectivity in addition reactions to the carbonyl group via metal exchange. Altogether, the homoaldol reactions now offer a general and reliable, highly stereoselective entry to γ-hydroxycarbonyl compounds, whereby the C(β)—C(γ) bond is formed. Furthermore, it is demonstrated how problems associated with the application of allyl anions as synthetic reagents can be solved today.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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