Description du sujet de thèse

Description of thesis topic “Cycloadditions of azines and their N-oxides”.

Diazines/triazines (and their N-oxides) have untapped potential as nitrogen-rich building blocks. The products of the reactions of these azines are N-heterocycles, making them ideal building blocks for life sciences and functional materials. As part of an ANR PRCI project (2024 edition) between France and the USA, the PhD student will explore the reactivity of diazines and triazines (and their N-oxides) in processes catalyzed by abundant metals and/or in organocatalytic processes. We will combine experimental and theoretical approaches to take advantage of their reactivity in nucleophilic reactions and in different types of cycloadditions. More specifically, the following points will be investigated in collaboration with the French and two American partners:

1. Reactivity: We will study the ionic and pericyclic reactions of N-oxides of diazines (1,3- and 1,4-) and triazines (1,2,3-). Inter- and intramolecular reactions will be studied, with particular emphasis on the differences in reactivity between oxidized and non-oxidized precursors. This initial study will provide a solid understanding of reactivity for the development of catalytic processes.

2. Selectivity: Catalytic Diels-Alder cycloadditions with inverse electron demand are generally difficult to achieve, and certain methodological gaps have yet to be filled in the case of di/tri-azines. Supported by preliminary results, catalytic approaches based on abundant metals and/or organo(photo)-catalysts will be investigated to favorably influence the rate and selectivities of ionic and pericyclic processes, but also to explore enantioselective transformations.

3. Mechanisms: In collaboration with one of our American partners, we will combine experimental and theoretical studies to improve our understanding of the reactions involved.

The PhD candidate
We are looking for a candidate with a Master's degree in Chemical Sciences, and very good theoretical and practical knowledge of synthetic and analytical chemistry. Written and oral communication skills, organizational skills and an interest in taking an active part in the day-to-day life of the laboratory are also expected. LIMA and the BSM team welcome students of all levels (from High School to post-doctoral associates), from France and abroad; the candidate should therefore have a team spirit and an interest in conducting research with colleagues from other backgrounds.

The candidate will acquire expertise in conducting research projects centered on organic synthesis through his/her thesis topic, but also through training courses, seminars and the use of electronic resources. The candidate will regularly present his/her results and those of recent literature in a critical way. He/she will have the opportunity to participate in congresses within the team's means. He/she could supervise trainee(s) of different levels (L3 to M2) by mutual agreement with the thesis supervisors.

The candidate must provide a letter of motivation, a detailed CV including a list of grades and the contact details of one (or two) reference(s).

Contexte de travail

The doctoral student will be enrolled in the Doctoral School of Chemical Sciences at the University of Strasbourg (ED222). Thesis work will be supervised by Dr. Nicolas Blanchard and Dr. Vincent Bizet (thesis co-directors, LIMA Laboratory, BSM team in Mulhouse, bsm.unistra.fr), in collaboration with Dr. Jean-François Brière's group (CARMEN Laboratory, Rouen) and the University of San Antonio in Texas (UTSA, USA, Pr. Michael Doyle and Pr. Oleg Larionov). The PhD student will have the opportunity to spend 15 to 30 days at UTSA during his or her PhD.

The doctoral student position at LIMA is in an area covered by a restricted zone, and therefore requires, in accordance with regulations, that your arrival be authorized by the defense security officer.

Le poste se situe dans un secteur relevant de la protection du potentiel scientifique et technique (PPST), et nécessite donc, conformément à la réglementation, que votre arrivée soit autorisée par l'autorité compétente du MESR.

Contraintes et risques

Not applicable