From homoallenyl aldehydes to proton sponges

Kód výsledku v 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>

Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

From homoallenyl aldehydes to proton sponges

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

From homoallenyl aldehydes to proton sponges

Popis výsledku anglicky

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.

Druh

O - Ostatní výsledky

CEP obor

CC - Organická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/GA203%2F09%2F1345" target="_blank" >GA203/09/1345: Allenový synthon v přípravě heterocyklických sloučenin</a><br>

Návaznosti

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

Rok uplatnění

2012

Kód důvěrnosti údajů

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