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From homoallenyl aldehydes to proton sponges

The result's identifiers

  • Result code in IS VaVaI

    <a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14310%2F12%3A00057492" target="_blank" >RIV/00216224:14310/12:00057492 - isvavai.cz</a>

  • Result on the web

  • DOI - Digital Object Identifier

Alternative languages

  • Result language

    angličtina

  • Original language name

    From homoallenyl aldehydes to proton sponges

  • Original language description

    Herein, we report a molecular framework design differing significantly from the traditional topology of proton sponges. We developed a suitable synthetic approach to the preparation of compounds with four fused five-membered rings from homoallenyl aldehydes by intramolecular criss-cross cycloaddition reactions of appropriate homoallenyl azines. The acid-catalyzed rearrangement of these cycloadducts afforded caged bidentate secondary amines in quantitative yields and following alkylation reactions led tofinal air nonsensitive highly stable substituted diazatetracyclo[4.4.0.13,10.15,8]dodecanes (DTDs) with rare alicyclic scaffolding in high overall yields. These molecules have two pairs of nitrogen atoms fixed in a configuration that guarantees acid-base properties similar to those of proton sponges. Their pKBH+ values were determined by 1H NMR transprotonation experiments as well as their sensitivity toward nucleophiles, acids and bases.

  • Czech name

  • Czech description

Classification

  • Type

    O - Miscellaneous

  • CEP classification

    CC - Organic chemistry

  • OECD FORD branch

Result continuities

  • Project

    <a href="/en/project/GA203%2F09%2F1345" target="_blank" >GA203/09/1345: Allenyl synthon in synthesis of heterocyclic compounds</a><br>

  • Continuities

    P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Others

  • Publication year

    2012

  • Confidentiality

    S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů