Mn(OAc)(3) catalyzed intermolecular oxidative peroxycyclization of naphthoquinone

Alex Meye Biyogo , Christophe Curti (1, 2) , Hussein El-Kashef (3) , Omar Khoumeri (1) , Thierry Terme (1) , Patrice Vanelle (1)

1 ICR - Institut de Chimie Radicalaire
2 APHM - Assistance Publique - Hôpitaux de Marseille
3 Department of Chemistry

Manganese(III) acetate-mediated peroxycyclization between 2-hydroxy-3-methylnaphthoquinone and various alkenes was performed to obtain dihydronaphtho[2,3-c][1,2] dioxine-5,10(3H, 10aH)-diones. The reactivity of symmetrical or unsymmetrical 1,1-disubstituted alkenes and monosubstituted alkenes allowed the synthesis of more than 50 original molecules. Focusing on the excellent reactivity of 2-hydroxy-3-methylnaphthoquinone, we describe the first example of Mn(OAc)(3) reactivity with nitro-substituted alkenes. The scope, limitations and stereochemistry of the products synthesized are discussed. Starting from monosubstituted alkenes, the instability of a pair of diastereoisomers was observed, leading to ring opening.

Mots clés: antimalarial; cyclic peroxides; derivatives; endoperoxides; in-vitro activity; manganese(iii) acetate; molecular-oxygen; plasmodium-falciparum; 1; 1-disubstituted alkenes; 2+2+2 cycloaddition

Domaines: Chimie

Alex Meye Biyogo, Christophe Curti, Hussein El-Kashef, Omar Khoumeri, Thierry Terme, et al.. Mn(OAc)(3) catalyzed intermolecular oxidative peroxycyclization of naphthoquinone. RSC Advances, 2017, 7 (1), pp.106--111. ⟨10.1039/c6ra25138b⟩. ⟨hal-01774203⟩