Synthesis of Substituted 1,4-Dioxenes through O–H Insertion and Cyclization Using Keto-Diazo Compounds

1,4-Dioxenes present interesting potential as synthetic intermediates and as unusual motifs for incorporation into biologically active compounds. Here, an efficient synthesis of functionalized 1,4-dioxenes is achieved in two steps. Using keto-diazo compounds, a ruthenium catalyzed O–H insertion with...

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Bibliographic Details
Published in:Journal of organic chemistry 2016-11, Vol.81 (22), p.11477-11488
Main Authors: Davis, Owen A, Croft, Rosemary A, Bull, James A
Format: Article
Language:English
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Summary:1,4-Dioxenes present interesting potential as synthetic intermediates and as unusual motifs for incorporation into biologically active compounds. Here, an efficient synthesis of functionalized 1,4-dioxenes is achieved in two steps. Using keto-diazo compounds, a ruthenium catalyzed O–H insertion with β-halohydrins followed by treatment with base results in cyclization with excellent selectivity, through O-alkylation of the keto–enolate. A variety of halohydrins and anion-stabilizing groups in the diazo-component are tolerated, affording novel functionalized dioxenes. Enantioenriched β-bromohydrins provide enantioenriched 1,4-dioxenes.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.6b02134