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Communication Dans Un Congrès Année : 2022

Prediction of superior enantioselectivity within a MOF

C. Mellot-Draznieks

Résumé

The last decade has seen an unprecedented progress in the discovery of new functional porous materials as well as the prediction of their properties. While the reactivity and enantioselectivity of molecular chiral catalysts have been rationalized and ultimately predicted for liquid-phase homogeneous phase reactions, asymmetric transformations associated to the increasing sophistication of MOF-based heterogeneous catalysts structures render computational efforts challenging. Here, in the case of asymmetric catalysis, the role of the MOF in confining the catalyst and in sterically constraining the approach of the substrate at the catalytic site is discussed. The specificities of host-guest interactions in the heterogeneous MOF-based catalyst when compared to those of molecular homogeneous counterparts are highlighted. We will show that computational chemistry can explain and even predict the selectivity in confined asymmetric catalysis within a MOF [1]. Computationally generated structures of Al-MIL-101-NH-Gly-Pro containing a benzene ruthenium complex as catalytically active site have been thoroughly analyzed for docking of prochiral substrate. The obtained data gave insights into enantioselective process at play inside the MOF and allowed to predict the selectivity of asymmetric transfer hydrogenation reaction catalyzed within the MOF. Experimentally, the heterogenization of a chiral benzene ruthenium molecular complex within the MIL-101-NH-Gly-Pro [2, 3] cavity allows a threefold enhancement of the selectivity in the catalyzed asymmetric transfer hydrogenation of acetophenone compared to homogenous analogue system. The excellent match between the computational outcomes and observed enantiomeric excesses provides a robust atomic-level rationale for the observed product selectivity. With these unpublished results, DFT-level computations supported by experimental data highlight the crucial role of the MOF as a macroligand [4] for the ruthenium catalyst to direct the enantioselectivity of the reaction. The molecular level understanding towards the prediction of structure-reactivity relationship in hybrid porous solids like MOF allows reaching the same level of rationalization in the design of heterogeneous catalyst than that developed for decades for molecular systems.[5] This work has been carried out within the French ANR projects HOPFAME (ANR-13-BS07-0002-01) and POMAC (ANR-18-CE07-0025-01). References 1.J. Canivet et al. Chem. Sci. 11, 8800–8808 (2020). 2.J. Bonnefoy et al., J. Am. Chem. Soc. 9409–9416 (2015). 3.T.K. Todorova et al., Chem. Eur. J. 22, 16531–16538 (2016). 4.F. M. Wisser et al. ACS Catal. 8, 1653–1661 (2018). 5.J.P. Reid et al., Nat. Rev. Chem. 2, 290 (2018).
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Dates et versions

hal-03770641 , version 1 (06-09-2022)

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  • HAL Id : hal-03770641 , version 1

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J. Canivet, C. Mellot-Draznieks. Prediction of superior enantioselectivity within a MOF. 8th International Conference on Metal-Organic Frameworks and Open Framework Compounds, Sep 2022, Dresden, Germany. ⟨hal-03770641⟩
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