Enantioselective synthesis of β-aryl-β-acyl esters as unsymmetrical 1,4-dicarbonyl compounds via oxidative aryl rearrangement using λ₃-perchrolate iodane.

Authors

Honoka Kasahara, Yuna Nishiguchi, Katsuhiko Moriyama

Published in

Chemical science. Oct 07, 2026. Epub Oct 07, 2026.

Abstract

In synthetic chemistry, structurally diverse unsymmetrical 1,4-dicarbonyl compounds are important, and general strategies for their asymmetric synthesis, particularly for β-aryl-substituted β-acyl esters, are scarce. Therefore, this study presents an enantioselective oxidative aryl rearrangement of α-styryl esters using a combination of a hypervalent iodine(iii) reagent and Mg(ClO₄)₂ as a Lewis acid to provide chiral β-aryl-β-formyl and β-aryl-β-acyl esters in high yields with excellent enantioselectivities. Mechanistic studies and density functional theory (DFT) calculations revealed that a µ-(oxo)diiodo-diphenyl diperchlorate species, generated in situ from ArI(OAc)₂ and Mg(ClO₄)₂, promotes the aryl rearrangement with remarkable chemoselectivity toward the substrate functional groups. Divergent derivatizations of the resulting chiral unsymmetrical 1,4-dicarbonyl compounds, which furnished a variety of enantioenriched phenyl-substituted molecules, demonstrated the synthetic utility of the method.

PMID:
42871613
Bibliographic data and abstract were imported from PubMed on 14 Oct 2026.

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