Entwicklung neuartiger Allensynthesen mit Chloropren-Grignard-Verbindungen

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Abstract: Die Addition von Chloropren-Grignards an Carbonylverbindungen führt zu Gemischen von Allenen und 1,3-Dienen. Die Selektivität dieser Addition konnte durch den Einsatz geeigneter Additive gesteuert werden. Durch Zugabe von Bis(dimethamino)diethylether (BDMAEE) zum Grignard erfolgt die anschließende Addition an aromatische Aldehyde bei tiefen Temperaturen mit bis zu 98% Ausbeute und durchweg exzellenter Regioselektivität. Die Addition an aliphatische Aldehyde gelingt durch vorherige Transmetallierung auf Aluminiumbinolat in guten Ausbeuten und ohne Bildung des 1,3-Diens.
Die Addition an aliphatische Aldehyde konnte über die Sequenz (i) Chloropren-Grignard Addition (ii) Pd-katalysierte syn-selektive Zyklisierung und (iii) Wacker-Oxidation genutzt werden und (1,3)n-Polyol Strukturen aufzubauen. N-Boc-Imine stellen ebenfalls geeignete Elektrophile für diese Reaktion dar, wobei für aromatische N-Boc-Imine der Einsatz von Dimorpholinodiethylether (DMDEE) eine hinreichend selektive Reaktion ermöglicht. Die Ausbeute- und Selektivitätsprobleme bei der Addition an aliphatische Imine konnten durch vorherige Transmetallierung auf Zink(II)bromid gelöst werden, was die aliphatischen beta-Allenylamine in 48-86% Ausbeute ohne Bildung des 1,3-Diens ermöglicht.
Die hergestellten beta-Allenylalkohole und beta-Allenylamine können in die entsprechenden Allenylsulfonylharnstoffe derivatisiert werden. Letztere wurden diastereokonvergent durch zwei sich ergänzende Katalysatorsysteme in die zyklischen syn- und anti-Harnstoffe überführt werden. Die zyklischen Harnstoffe bilden dabei ausgezeichnete Ausgangsmaterialien für weitere Funktionalisierungen oder können in die diastereomer angereicherten 1,3-Amine entschützt werden.
Schließlich wurden verscheidene Ansätze zur Darstellung von Ascaulitoxin Aglycon erprobt. Der Aufbau der nicht-proteinogenen Aminosäure durch die Schöllkopf-Methode konnte durch Cu(I)-katalysierte Allenylierung von Iodalanin verbessert werden. Durch die Addition von Chloropren-Grignard an den Allenylaminosäureester abgeleiteten Aldehyd konnte ein vielversprechender Vorläufer für eine doppelte katalysierte Zyklisierung hergestellt werden, die ohne Erfolg blieb, jedoch einen vielversprechenden Ansatzpunkt für die schrittweise Synthese von Ascaulitoxin darstellt

Location: Deutsche Nationalbibliothek Frankfurt am Main

Extent: Online-Ressource

Language: Deutsch

Notes: Universität Freiburg, Dissertation, 2022

Keyword: Chemische Synthese
Asymmetrische Synthese
Allenderivate
Organische Chemie
Homogene Katalyse
Naturstoffchemie

Event: Veröffentlichung

(where): Freiburg

(who): Universität

(when): 2023

Creator: Geissler, Arne G. A.

Contributor: Breit, Bernhard
Jessen, Henning Jacob
Albert-Ludwigs-Universität Freiburg. Institut für Organische Chemie
Albert-Ludwigs-Universität Freiburg. Fakultät für Chemie und Pharmazie

DOI: 10.6094/UNIFR/232579

URN: urn:nbn:de:bsz:25-freidok-2325796

Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.

Last update: 15.08.2025, 7:39 AM CEST

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Design of sensors for highly phosphorylated natural compounds

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Novel shades of inositol pyrophosphates – in vitro and in cellulo evaluation of inositol pyrophosphate probes

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Design of sensors for highly phosphorylated natural compounds

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Entwicklung neuartiger Allensynthesen mit Chloropren-Grignard-Verbindungen

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Novel shades of inositol pyrophosphates – in vitro and in cellulo evaluation of inositol pyrophosphate probes

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