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1,2-Dioxines as Masked Cis γ-Hydroxy Enones and Their Versatility in the Synthesis of Highly Substituted γ-Lactones

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Ben W. Greatrex,^† Marc C. Kimber,^† Dennis K. Taylor,*^† Gary Fallon,^‡ and Edward R. T. Tiekink^§

Department of Chemistry, University of Adelaide, S.A., Australia, 5005, School of Chemistry, Monash University, Vic., Australia, 3800, and Department of Chemistry, National University of Singapore, Singapore, 117543

J. Org. Chem., 2002, 67 (15), pp 5307–5314

DOI: 10.1021/jo0200421

Publication Date (Web): June 26, 2002

Abstract

Addition of highly stabilized ester nucleophiles to 1,2-dioxines affords good to high yields of γ-lactones with high diastereoselectivity. Heterolytic or homolytic cleavage of the 1,2-dioxines under appropriate conditions generates the key reactive cis γ-hydroxy enones, which ultimately afford the observed γ-lactones. Diastereoselectivity is installed as a result of anti 1,4-addition by the ester enolate to the cis enones followed by intramolecular cyclization. The reaction is tolerant of a range of substitution patterns on the 1,2-dioxine while a broad range of esters are also accommodated. In addition to the synthesis of racemic γ-lactones, highly enantioenriched γ-lactones can also be synthesized when chiral cobalt(II) catalysts are employed for the initial homolytic ring-opening of the 1,2-dioxine.

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Published In Issue July 26, 2002
Received January 18, 2002

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Article

1,2-Dioxines as Masked Cis γ-Hydroxy Enones and Their Versatility in the Synthesis of Highly Substituted γ-Lactones

Abstract

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