1,2-Dioxines as Masked Cis γ-Hydroxy Enones and Their Versatility in the Synthesis of Highly Substituted γ-Lactones
- 26 June 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 67 (15) , 5307-5314
- https://doi.org/10.1021/jo0200421
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.Keywords
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