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l-proline modulated zirconium metal organic frameworks: Simple chiral catalysts for the aldol addition reaction

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Abstract Three l -proline modulated zirconium based MOFs denoted as UiO-66, Zr-NDC (NDC = 2,6-Naphthalenedicarboxylate) and UiO-67 were synthesized, characterized and explored as heterogeneous catalyst in diastereoselective aldol addition reactions between 4-nitrobenzaldehyde… Click to show full abstract

Abstract Three l -proline modulated zirconium based MOFs denoted as UiO-66, Zr-NDC (NDC = 2,6-Naphthalenedicarboxylate) and UiO-67 were synthesized, characterized and explored as heterogeneous catalyst in diastereoselective aldol addition reactions between 4-nitrobenzaldehyde and linear/cyclic ketones. Upon l -proline modulation, chirality was introduced into these Zr-MOFs which were consequently explored as chiral catalysts for asymmetric reactions. A systematic study was conducted to look into the effect of the synthesis temperature on the modulation in each Zr-MOF. The modulated UiO-66 material synthesized at 120 °C exhibited full conversion and a good diastereoselectivity whereas the homogeneous l -proline catalyst showed only 61% conversion and a reversed diastereoselectivity. The catalyst exhibited no leaching of the catalytically active species and was reused for at least three additional cycles. The observed high catalytic activity is a result of the electron withdrawing nature of the Zr-node coordinated to l -proline.

Keywords: chiral catalysts; proline modulated; proline; modulated zirconium; aldol addition

Journal Title: Journal of Catalysis
Year Published: 2018

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