Organocatalytic asymmetric peroxidation of g,d-unsaturated ß-keto esters - A novel route to chiral cycloperoxides

Hennessy, Mary C.; Hirenkumar, Gandhi; O'Sullivan, Timothy P.

Organocatalytic asymmetric peroxidation of g,d-unsaturated ß-keto esters - A novel route to chiral cycloperoxides

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Files

molecules-28-04317-v2.pdf(2.96 MB)

Published version

molecules-28-04317-s001.zip(11.61 MB)

Date

2023-05-24

Authors

Hennessy, Mary C.

Hirenkumar, Gandhi

O'Sullivan, Timothy P.

Published Version

10.3390/molecules28114317

Abstract

A methodology for the asymmetric peroxidation of g,d-unsaturated ß-keto esters is presented. Using a cinchona-derived organocatalyst, the target d-peroxy-ß-keto esters were obtained in high enantiomeric ratios of up to 95:5. Additionally, these d-peroxy esters can be readily reduced to chiral d-hydroxy-ß-keto esters without impacting the ß-keto ester functionality. Importantly, this chemistry opens up a concise route to chiral 1,2-dioxolanes, a common motif in many bioactive natural products, via a novel P2O5-mediated cyclisation of the corresponding d-peroxy-ß-hydroxy esters.

Keywords

Cycloperoxides , Organocatalysis , δ-peroxy-β-keto esters , δ-hydroxy-β-keto esters , 1,2-dioxolanes

Citation

Hennessy, M.C., Gandhi, H. and O’Sullivan, T.P. (2023) ‘Organocatalytic asymmetric peroxidation of γ,δ-unsaturated β-keto esters—a novel route to chiral cycloperoxides’, Molecules, 28(11), 4317 (12 pp). https://doi.org/10.3390/molecules28114317.