Synthesis 2003(5): 0668-0672
DOI: 10.1055/s-2003-38073
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

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

Ben Greatrexa, Martyn Jevrica, Marc C. Kimbera, Sara J. Krivickasa, Dennis K. Taylor*a, Edward R. T. Tiekinkb
a Department of Chemistry, University of Adelaide, South Australia, Australia, 5005.
Fax: +61(8)83034358; e-Mail: dennis.taylor@adelaide.edu.au;
b Department of Chemistry, National University of Singapore, Singapore, 117543.
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Publikationsverlauf

Received 21 October 2002
Publikationsdatum:
21. März 2003 (online)

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.

7

Krivickas, S. J.; Taylor, D. K. 2001, unpublished results.

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