Description

Over the last decades, the borrowing hydrogen (BH) methodology has emerged as an attractive strategy for the construction of novel CN bonds from an alcohol and an amine. This one-pot process involves a catalytic reduction of an unreactive alcohol into a carbonyl, followed by in situ imine formation and subsequent reduction. Metals such as Ir, Ru, Fe and Mn enable this transformation with water as the sole by-product.
In recent years, our group has applied this strategy for the valorization of bio-based alcohols, such as isohexides and 1,4-D-sorbitan, to access chiral amines and amino alcohols.
Despite significant advances reported in the literature, access to chiral saturated N-heterocycles via the BH methodology remains a major synthetic challenge. The first objective of this PhD project will focus on the synthesis of chiral substituted piperidines and pyrrolidines directly from racemic triols
The second objective of the project will exploit the BH process for the preparation of polyhydroxypyrrolidines and piperidines from biomass-derived polyols

Compétences requises

The PhD student will develop strong expertise in synthetic methodology and the structural characterization of chiral molecules. Although in full charge of the operational part, he or she will benefit from a participatory, reliable and guiding management from a close-knit team, with common processes and attached with the same care for quality. This constant support to autonomy and innovation will be reinforced by written and oral communication competencies. A solid background in synthetic organic chemistry and experience in NMR ( 1H, 13C and 2D) structural characterization will be appreciated. Overall, we are seeking a motivated, reliable and well-organized candidate who values teamwork.

Bibliographie

a) M. Jacolot, S. Moebs-Sanchez, F. Popowycz, J. Org. Chem. 2018, 83, 9456–9463.
b) F. Bahé, L. Grand, E. Cartier, M. Jacolot, S. Moebs-Sanchez, D. Portinha, E. Fleury, F.
Popowycz, Eur. J. Org. Chem. 2020, 2020, 599–608.
c) L. Grand, M. Powderly, F. Popowycz, M. Jacolot, J. Org. Chem. 2023, 88, 2642–2647.
d) M. Jacolot, F. Popowycz, Eur J Org Chem 2024, 27, e202301119.
e) M. Larduinat, J. François, M. Jacolot and F. Popowycz, J. Org. Chem., 2023, 88, 7512–7517.
f) J. François, M. Jacolot, F. Popowycz, Org. Biomol. Chem. 2024, 22, 4502–4507

Mots clés

synthèse organique, catalyse homogène, alcool biosourcé