Ir-Na Cooperativity Controls the Diastereoselectivity of Borrowing Hydrogen C-C Alkylation on Isosorbide: Synthesis Methodology and Mechanistic Investigation - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Organic Chemistry Frontiers Année : 2023

Ir-Na Cooperativity Controls the Diastereoselectivity of Borrowing Hydrogen C-C Alkylation on Isosorbide: Synthesis Methodology and Mechanistic Investigation

Résumé

The direct functionalization of isosorbide is a curent challenge of biomass valorisation due to the low selectivities usually obtained. Taking advantage of our preliminary observations concerning the diastereoselective Ir-catalyzed amination of isohexides we report the first direct CC borrowing hydrogen direct functionalisation on isosorbide. The CC alkylation was achieved with excellent diastereocontrol using an Ir-based organometallic homogeneous catalyst. The reaction sequence involves a catalytic dehydrogenation that converts the alcohol into a reactive ketone, the in situ aldol condensation / crotonisation, and a catalytic dehydrogenation leading to the homologated desired product. Once the parameters that control the reaction outcome were explored and optimized, the stereoelectronic effects from which the diastereoselectivity originates from have been investigated by means of a computional mechansitic performed at the DFT level. The roles played by the Na counter-cation to coordinate substrate's oxygen atoms and to guide hydride addition were evidenced allowing to rationalize the experimental selectivity at the molecular level.
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Dates et versions

hal-04285559 , version 1 (14-11-2023)

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Jordan François, Jordan Rio, Erwann Jeanneau, Marie-Ève L Perrin, Maïwenn Jacolot, et al.. Ir-Na Cooperativity Controls the Diastereoselectivity of Borrowing Hydrogen C-C Alkylation on Isosorbide: Synthesis Methodology and Mechanistic Investigation. Organic Chemistry Frontiers, 2023, 10 (19), pp.4732-4739. ⟨10.1039/D3QO00700F⟩. ⟨hal-04285559⟩
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