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Nanocausys project

funded by ANR CD2I

The project Nanocausys (Nanostructured catalysts in unconventional systems), involving 5 French academic laboratories (ICN, ISM, ICMCB, ICCF, LOF) and the European chemical company Solvay (via E2P2L), is funded by ANR program “Sustainable Chemistry, Industry, Innovation”. This project is aimed at demonstrating the feasibility of heterogeneous catalysis in continuous reactors for industrial applications. We have chosen an integrated approach taking into account matrix, catalysts and reactor designs through the combined expertise of scientists from material science, catalysis and biocatalysis, microfluidics and reactor engineering. Nanostructured catalysts will be used in 3 categories of coupling reactions, implemented in continuous reactors, and eventually applied industrially in the synthesis of biosourced ingredients.

ICN : Institut de Chimie de Nice (U. Nice Sophia Antipolis - CNRS)
ISM : Institut des Sciences Moléculaires (U. Bordeaux - CNRS)
IICMCB : Institut de Chimie de la Matière Condensée de Bordeaux (U. Bordeaux - CNRS)
ICCF : Institut de Chimie de Clermont-Ferrand (U. Clermont-Ferrand - CNRS)
LOF : Laboratory of the Future (U. Bordeaux - CNRS - Solvay)
E2P2L : Eco-Efficient Products & Processes Laboratory (CNRS - Solvay - ENS Lyon - East China Normal University)

Hydroalkoxylation of olefins

Collab. with Dr Mathieu Pucheault - ISM Bordeaux

The transfer of catalytic hydroalkoxylation reactions of olefins from homogeneous to heterogeneous conditions has been studied using Montmorillonite (MMT) doped with metal cations. In the case of intramolecular reactions, 38-99% yields of cyclic ethers have been obtained using Fe-MMT and Bi-MMT both in CH3NO2 and dimethylcarbonate (DMC) compared with other supported metals salts or metal nanoparticles. In the case of more challenging intermolecular reactions, conversions up to 72% and yields up to 54% were obtained with metal-doped MMT as well, such as Fe-, Bi-, and Ti-MMT. These catalytic systems were shown to be highly recyclable and amenable to flow chemistry.

I. Notar Francesco, B. Cacciuttolo, M. Pucheault, S. Antoniotti. Simple metal salts supported on Montmorillonite as recyclable catalysts for intramolecular hydroalkoxylation of double bonds in conventional and VOC exempt solvents. Green Chem. 2015, 17 (2), 837 - 841. Link.

I. Notar Francesco, B. Cacciuttolo, O. Pascu, C. Aymonier, M. Pucheault, S. Antoniotti. Simple salts of abondant metals (Fe, Bi, and Ti) supported on Montmorillonite as efficient and recyclable catalysts for regioselective intramolecular and intermolecular hydroalkoxylation reactions of double bonds and tandem processes. RSC Advances, 2016, 6, 19807 - 19818. Link.

AuNPs project

The project AuNPs is aimed at developing novel atom- and step-economic reactions catalysed by metal nanoparticles. The philosophy is to merge homogenous and heterogeneous catalysis to get the advantages of both (basically selectivity and recyclability).

Minireview article : I. Notar Francesco, F. Fontaine-Vive, S. Antoniotti. Synergies in the catalytic activity of bimetallic nanoparticles and new synthetic methods for the preparation of fine chemicals. ChemCatChem, 2014, 6, 10, 2784-2791. Link.

Novel radical tandem 1,6-enynes thioacylation / cyclisation catalysed by Au-Pd nanoparticles

Collab. with Prof. Graham J. Hutchings - Cardiff Catalysis Institute

We studied the reactivity of 1,6-enynes with thioacetic acid (AcSH) under either thermal conditions or in the presence of catalytic amounts of supported Au or Au-Pd nanoparticles (NPs) under mild conditions. The 1,6-enynes undergo a tandem thioacylation / cyclisation to original cyclic products featuring either a homoallylic thioester function or an enol thioester function depending on the substrate topology. Interestingly, the former process was found more efficient when performed in the presence of Au-Pd NPs while the latter process can be efficiently carried out under thermal conditions (100 °C). The reaction proceeds by a radical mechanism and the presence of precious metal NPs seems to stabilise the formation of free radical intermediates, as supported by experimental and theoretical results.

I. Notar Francesco, J. Giauffret, F. Fontaine-Vive, J. K. Edwards, C. J. Kiely, G. J. Hutchings, S. Antoniotti. Novel radical tandem 1,6-enynes thioacylation / cyclisation : Au-Pd nanoparticles catalysis versus thermal activation as a function of the substrate specificity. Tetrahedron, 2014, 70, 51, 9635–9643. Link.

Multicatalytic reactions en route to the one-pot total synthesis of complex molecules

A current project we are working on deals with the setup of multicatalytic reactions, either fully orthogonal, sequential one-pot or in continuous flow. A first example was recently published with an easy access to chromene and 1,2-dihydroquinoline derivatives from simple substrates catalysed by Au NPs and simple bases.

P. D. Giorgi, P. J. Miedziak, J. K. Edwards, G. J. Hutchings, S. Antoniotti. Bicatalytic multistep reactions en route to the one-pot total synthesis of complex molecules : easy access to chromene and 1,2-dihydroquinoline derivatives from simple substrates. ChemCatChem 2017, 9, 1, 70-75.. Cover picture. Link. Highlighted by Wiley in Hot topics : sustainable chemistry.

P. D. Giorgi, N. Elizarov, S. Antoniotti. Selective oxidation of activated alcohols by supported gold nanoparticles under an atmospheric pressure of O2 : batch and continuous flow studies. ChemCatChem 2017, accepted article DOI : 10.1002/cctc.201700179. Link.

Innovative fragrant ingredients

Review article : S. Antoniotti. Tuning of essential oils properties by enzymatic treatment : Towards sustainable processes for the generation of new fragrant ingredients. Molecules, 2014, 19(7), 9203-9214. (Invitation) OPEN ACCESS.

Essenzyme project

Labelised by cluster PASS

Funded by APRF CR PACA

The project Essenzyme is a collaborative project between our group and two French companies, aimed at developping mild enzymatic protocols for the tuning of essential oils properties by modification of their chemical composition. It is divided in several sub-projects, one for the design of novel fragrance ingredients, and the second for the production of detoxified essential oils.

Natural vetiver acetate project

Funded by SATT sud-est

Development of an industrial process for the manufacture of natural vetiveryl acetate for the perfume industry.

I. Notar Francesco, J.-J. Filippi, S. Antoniotti. Sustainable manufacture of a valuable fragrance ingredient : Lipase-catalysed acylation of vetiver essential oil and chemoselectivity between sesquiterpene alcohols. ChemPlusChem, 2017, early view. DOI : 10.1002/cplu.201600617. Link. Highlighted in the Wiley Hot topics : biocatalysis.

Natural atranol-free oakmoss extracts

Funded by SATT sud-est

Development of an enzymatic process for the removal of atranol and related toxic compounds from oakmoss extracts.

GDRO3 : French transdisciplinary research network on odorants, odours and olfaction