ESR2 Project

Design of efficient catalytic tools for a direct access to chiral amines

Recruting institution: URV
Diploma-delivering institutions: URV, INPT
Thesis co-directors: Cyril Godard (URV, Tarragona, ES), Martine Urrutigoity (LCC, Toulouse, FR)
Secondment host: Italmatch Chemicals (IT)
Academic secondment : DTU

Objectives
Chiral amines are efficient functional components in fine chemistry to attain pharmaceutical and agrochemical active products [1]. For their production, an elegant and environmentally benign alternative to multistep classical organic synthetic routes is provided by the one-pot hydroaminomethylation reaction, (HAM) [2]. This project aims at the development of efficient catalysts for the asymmetric version of the HAM, which has not been reported to date using a single catalyst. The reaction will be investigated in two parallel approaches including the study of asymmetric hydroformylation/reductive amination and hydroformylation/amine condensation/asymmetric hydrogenation (of imines or enamines). The most efficient catalysts will be subsequently immobilised onto carbon supports to study their recycling and their performance under continuous flow conditions.
Expected Results
Efficient chiral catalysts for HAM of alkenes will be designed and developed aiming at complete conversion of the substrates, high chemoselectivity to the final amines (at least 90%) with ≥ 90% ee. Structure/ performance relationships will be obtained through mechanistic studies using high pressure techniques (HP-NMR, HP-IR, …). The robustness of the most efficient catalysts will be evaluated through their immobilisation and subsequent recycling studies and testing under continuous flow conditions (in collaboration with Pr. Anders Riisager at DTU).

[1] Y. Yamamoto, U. Radhakrishnan, Chem. Soc. Rev.1999, 28, 199–207.
[2] a) D. Crozet, A. Gual, D. McKay, C. Dinoi, L. Maron, C. Godard, J.-C. Daran, M. Urrutigoïty, Ph. Kalck, C. Claver Chem. Eur. J.2012, 18, 7128-7140; b) P. Kalck, M. Urrutigoïty Chem. Rev. 2018, 118, 3833-3861.