A Novel bis-Lactonisation of Naphtho- and Phenanthro-1,2-Dioxines with Malonate­ Nucleophiles

Abstract

Malonate nucleophiles add in a conjugate fashion to substituted naphtho- and phenanthro-1,2-dioxines to furnish functionalised bis-lactones in high yield and with high de. The basicity of the malonate nucleophile is sufficiently mild to rearrange the 1,2-dioxines to yield the transient cis-γ-hydroxy enone species with no further Kornblum-DeLaMare rearrangement. The cis-γ-hydroxy enones readily undergo conjugate addition by malonate nucleophiles in a highly diastereoselective fashion. An intramolecular domino cyclisation then ensues yielding the observed bis-lactones. The relative configuration of the bis-lactone series was established by 1- and 2-D ¹H, ¹³C NMR techniques and further confirmed by single crystal X-ray analysis.

Key words

bis-lactones - peroxides - cis-γ-Hydroxy enones - domino reactions - michael additions

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7

Krivickas, S. J.; Taylor, D. K. 2001, unpublished results.

10

Greatrex, B.; Jevric, M.; Kimber, M. C.; Krivickas, S. J.; Taylor, D. K.; Tiekink, E. R. T. Z. Kristallogr. 2002, 217, 587.