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

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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