Faculté des Sciences
Faculté des Sciences

Innovative strategy towards (bicyclo)-3,6-dihydro-1,2-oxazines from a novel class of photocleavable acylnitroso

Tilmant, Thomas ULiège
Promotor(s) : Monbaliu, Jean-Christophe ULiège
Date of defense : 9-Sep-2019 • Permalink :
Title : Innovative strategy towards (bicyclo)-3,6-dihydro-1,2-oxazines from a novel class of photocleavable acylnitroso
Translated title : [fr] Stratégie novatrice pour la préparation de (bicyclo)-3,6-dihydro-1,2-oxazines à partir d'une nouvelle classe d'acylnitroso photolabile
Author : Tilmant, Thomas ULiège
Date of defense  : 9-Sep-2019
Advisor(s) : Monbaliu, Jean-Christophe ULiège
Committee's member(s) : Detrembleur, Christophe ULiège
Luxen, André ULiège
Damblon, Christian ULiège
Language : English
Number of pages : 135
Keywords : [en] hydroxycarbamate
[en] acylnitroso
[en] oxazines
[en] photochemistry
[en] continuous flow
Discipline(s) : Physical, chemical, mathematical & earth Sciences > Chemistry
Research unit : Center for Integrated Technology and Organic Synthesis
Target public : Researchers
Professionals of domain
Institution(s) : Université de Liège, Liège, Belgique
Degree: Master en sciences chimiques, à finalité approfondie
Faculty: Master thesis of the Faculté des Sciences


[en] The present research project is devoted to the preparation of polyfunctional (bicyclo)-3,6-dihydro-1,2-oxazine scaffold (OS) bearing a free amine through a nitroso hetero Diels Alder (nHDA) reaction using a novel class of photocleavable acylnitroso compound followed by the orthogonal removal of the photolabile moiety. We successfully developed a 3-step strategy to reach the coveted OS. In the first step, we obtained the key hydroxycarbamate precursor in 81% yield and >99% purity, which is composed of two parts: a nitropiperonyl based photolabile copula and the N-hydroxycarbamate. This precursor was subsequently oxidized to yield a highly reactive nitroso dienophile species to perform various nHDA reactions using a small diene library. Among the oxidation procedures employed, H2O2 in the presence of CuCl afforded the best results with yields and purities ranging from 78-86% and 84-97%, respectively. We have also designed a new promising procedure for the precursor photooxidation under continuous flow conditions. Finally, the targeted OS bearing a free amine was obtained after irradiating the cycloadduct at 365 nm for 30 s under continuous flow conditions. The results obtained demonstrated the feasibility as well as the potency and robustness of our novel strategy for the preparation of a multitude of OS bearing a free amine.



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  • Tilmant, Thomas ULiège Université de Liège > Master en sc. chimiques, à fin.


Committee's member(s)

  • Detrembleur, Christophe ULiège Université de Liège - ULiège > Département de chimie (sciences) > Centre d'études et de rech. sur les macromolécules (CERM)
    ORBi View his publications on ORBi
  • Luxen, André ULiège Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie organique de synthèse
    ORBi View his publications on ORBi
  • Damblon, Christian ULiège Université de Liège - ULiège > Département de chimie (sciences) > Chimie biologique structurale
    ORBi View his publications on ORBi
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  • Total number of downloads 11

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