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Communication Dans Un Congrès Année : 2022

Urea-based foldamer catalyst for C-C bond forming in asymmetric Michael reaction : a DFT investigation

Résumé

Bioinspired urea-based oligomers that fold with high fidelity (foldamers (F)) have been proven 1 as robust alternatives to metal basedasymmetric catalysis, able to catalyze challenging C-C bond forming reactions with high enantioselectivity, and loadings as low as 1:10000 chiral catalyst/substrates molar ratios. However, studies developed at the atomistic level are necessary to understand the characteristics and function of the foldamers as catalysts. A DFT based Global Optimization procedure has been performed to find the low lying molecular arrangement in the conjugate addition of dimethylmalonate (M) to (1E)-3-methyl-1-nitrobut-1-ene (N) (see Figure below). It was found that N prefer the second site as H-bond donor, and M the first site. The interactions stabilizing the system are mainly electrostatic and noncovalent, with a set of Van der Waals interactions well defined between N and the phenyl group in F. Further investigations have been made in the Transition States, and the enantiomer R was predominant over the enantiomer S, which is coincident with the experimental observations. The enantiocontrol is identified to be related with specific geometrical parameters of the catalyst. These results rationalize the structure-properties relationship of the catalyst, and present for the first time a conclusive identification of its function. Further improvements to the catalytic properties of F-like foldamers are now possible.
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Dates et versions

hal-03812440 , version 1 (14-10-2022)

Identifiants

  • HAL Id : hal-03812440 , version 1

Citer

Yaidel Toledo-Gonzalez, Gilles Guichard, Jean-Marc Sotiropoulos, Philippe Carbonnière. Urea-based foldamer catalyst for C-C bond forming in asymmetric Michael reaction : a DFT investigation. Les journées de la Société Chimique de France dans le Grand Sud-Ouest, Jul 2022, Toulouse, France. ⟨hal-03812440⟩
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