Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

Synthesis of C3-Symmetric Cinchona-Based Organocatalysts and Their Application in Asymmetric Michael and Friedel–Crafts Reactions

Version 1 : Received: 28 February 2021 / Approved: 2 March 2021 / Online: 2 March 2021 (10:39:11 CET)

A peer-reviewed article of this Preprint also exists.

Kisszékelyi, P.; Fehér, Z.; Nagy, S.; Bagi, P.; Kozma, P.; Garádi, Z.; Dékány, M.; Huszthy, P.; Mátravölgyi, B.; Kupai, J. Synthesis of C3-Symmetric Cinchona-Based Organocatalysts and Their Applications in Asymmetric Michael and Friedel–Crafts Reactions. Symmetry 2021, 13, 521. Kisszékelyi, P.; Fehér, Z.; Nagy, S.; Bagi, P.; Kozma, P.; Garádi, Z.; Dékány, M.; Huszthy, P.; Mátravölgyi, B.; Kupai, J. Synthesis of C3-Symmetric Cinchona-Based Organocatalysts and Their Applications in Asymmetric Michael and Friedel–Crafts Reactions. Symmetry 2021, 13, 521.

Journal reference: Symmetry 2021, 13, 521
DOI: 10.3390/sym13030521

Abstract

In this work, anchoring of cinchona derivatives to trifunctional cores (hub approach) was demonstrated to obtain size-enlarged organocatalysts. By modifying the cinchona skeleton in different positions, we prepared four C3-symmetric size-enlarged cinchona derivatives (hub-cinchonas), which were tested as organocatalysts and their catalytic activities were compared with the parent cinchona (hydroquinine) catalyst. We showed that in the hydroxyalkylation reaction of indole, hydroquinine provides good enantioselectivities (up to 73% ee), while the four new size-enlarged derivatives gave significantly lower values (up to 29% ee) in this reaction. Anchoring cinchonas to trifunctional cores was found to facilitate nanofiltration-supported catalyst recovery using PolarClean alternative solvent. The C3-symmetric size-enlarged organocatalysts were completely rejected by all the applied membranes, whereas the separation of hydroquinine was found to be insufficient using organic solvent nanofiltration. Furthermore, the asymmetric catalysis was successfully demonstrated in the case of Michael reaction of 1,3-diketones and trans-β-nitrostyrene using Hub3-cinchona (up to 96% ee) as a result of the positive effect of the C3-symmetric structure using a bulkier substrate. This means an increased selectivity of the catalyst in comparison to hydroquinine in the latter Michael reaction.

Subject Areas

cinchona; organocatalysis; C3-symmetry; size-enlargement; nanofiltration; asymmetric reaction

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