Biphenyl-Based Bis(thiourea) Organocatalyst for Asymmetric and syn-Selective Henry Reaction

Jan Otevrel; Pavel Bobal

doi:10.1055/s-0036-1588594

Synthesis, Table of Contents

Synthesis 2017; 49(03): 593-603
DOI: 10.1055/s-0036-1588594

paper

Biphenyl-Based Bis(thiourea) Organocatalyst for Asymmetric and syn-Selective Henry Reaction

Jan Otevrel

Department of Chemical Drugs, Faculty of Pharmacy, University of Veterinary and Pharmaceutical Sciences Brno, Palackeho 1946/1, 612 42 Brno, Czech Republic Email: bobalp@vfu.cz

,

Pavel Bobal*

Department of Chemical Drugs, Faculty of Pharmacy, University of Veterinary and Pharmaceutical Sciences Brno, Palackeho 1946/1, 612 42 Brno, Czech Republic Email: bobalp@vfu.cz

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Abstract

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Abstract

A scalable, efficient and chromatography-free synthesis of a new enantiopure C ₂-symmetric bis(thiourea) catalyst was accomplished from a readily available starting material. The developed strategy could be conducted on a multi-gram scale. Both the prepared enantiomers of the bis(thiourea) organocatalyst have been tested in the asymmetric Henry reaction under thoroughly optimized conditions during which an unusual solvent effect on enantioselectivity was found. The corresponding adducts were obtained in excellent yields with good to excellent enantioselectivities. The achieved high reactivity and enantioselectivity in the nitroaldol reaction of nitroalkanes with aromatic aldehydes suggests promising potential for this catalyst. Moreover, a significant syn-diastereoselectivity was observed.

Key words

organocatalysis - asymmetric Henry reaction - chiral bis(thiourea) - chiral Brønsted acid catalysis - syn-diastereoselectivity

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References

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Supplementary Material

Supporting Information