Development of innovative stereoselective methodologies via phosphine organocatalysis and gold(I) catalysis
Séminaire Chimie ED459
Dr. Arnaud
Le Jeudi 19 Octobre 2023 à 15h
CNRS, Amphithéâtre Balard (bâtiment Balard RdC, 1919 route de Mende)
Date de début : 2023-10-19 15:00:00
Date de fin : 2023-10-19 16:30:00
Lieu : CNRS amphi Balard
Intervenant : Dr. Arnaud
ICSN Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Gif-s/-Yvette
Two projects recently developed in the group will be presented, which have in common the development of new stereoselective methodologies for the synthesis of bioactive compounds and/or natural products.
The first topic will concern the development of organocatalytic (and asymmetric) processes via P(III)/P(V) redox cycling. Tertiary phosphines play a crucial role as stoichiometric reagents in a variety of reactions, daily used in organic synthesis. Despite their usefulness, these venerable reactions suffer from several drawbacks, including the concomitant formation of phosphine oxide. In order to address these concerns, it was envisaged to use a substoichiometric quantity of phosphine, via a strategy involving in situ phosphine oxide reduction with organosilane. In this context, the first enantioselective phosphine-catalyzed Michael addition/Wittig olefination reaction was developed, for the synthesis of nitrogen-containing heterocycles, chiral (trifluoromethyl)cyclobutenes and spirocyclic derivatives.[1]
In a second part, the asymmetric synthesis of cyclopentenones with C4-quaternary stereocenters has been developed, through a stereospecific gold-catalyzed [3,3]-sigmatropic rearrangement. The application of this simple methodology allowed the total synthesis of many natural sesquiterpenoids, including hitoyopodin A, lagopodin A, isocuparene-3,4-diol and enokipodin A and B.[2]
References
1. a) C. Lorton, T. Castanheiro, A. Voituriez, J. Am. Chem. Soc. 2019, 141, 10142; b) C. Lorton, A. Roblin, P. Retailleau, A. Voituriez, Adv. Synth. Catal. 2021, 363, 4805; c) R. Losa, C. Lorton, P. Retailleau, J. Bignon, A. Voituriez, Org. Lett. 2023, 25, 5140.
2. a) W. Zhou, A. Voituriez, J. Am. Chem. Soc. 2021, 143, 17348; b) W. Zhou, A. Voituriez, Org. Lett. 2021, 23, 247; c) W. Zhou, A. Voituriez, Eur. J. Org. Chem. 2023, 26, e202300126; d) W. Zhou, A. Voituriez, ChemRxiv 2022, preprint, DOI: 10.26434/chemrxiv-2022-qkrrh
Contact local ICGM : Dr. Tahar
