Oxidation of 1-Arylcyclohexa-2,5-dienes and Subsequent Double Michael Addition. A Rapid Access to the Büchi Ketone and the Pentacyclic Core of Aspidosperma Alkaloids

Dawood Hosni Ibrahim (1) , Julie Dunet (1) , Frédéric Robert (1) , Yannick Landais (1)

1 ISM - Institut des Sciences Moléculaires

The Pd-catalyzed oxidation of 1-arylcyclohexa-2,5-dienes, resulting from a Birch reductive alkylation, leads to the corresponding arylcyclohexadienones. A careful choice of the substituents on the starting biaryl affords arylcyclohexadieonones, which may then enter into a double Michael addition, opening an access to the tetracyclic core of terpene indole alkaloids of the aspidosperma family. This strategy was used to prepare the Büchi ketone, a key-intermediate in the synthesis of this class of alkaloids, in 6 synthetic operations and 17% overall yield from commercially available 2aminobiphenyl.

Domaines: Chimie organique

Dawood Hosni Ibrahim, Julie Dunet, Frédéric Robert, Yannick Landais. Oxidation of 1-Arylcyclohexa-2,5-dienes and Subsequent Double Michael Addition. A Rapid Access to the Büchi Ketone and the Pentacyclic Core of Aspidosperma Alkaloids. Heterocycles, 2018, 97 (1), pp.459. ⟨10.3987/COM-18-S(T)36⟩. ⟨hal-02378441⟩