Dichlorination of α-Diazo-β-dicarbonyls Using (Dichloroiodo)benzene

Keith E. Coffey; Graham K. Murphy

doi:10.1055/s-0034-1380304

Synlett, Table of Contents

Synlett 2015; 26(08): 1003-1007
DOI: 10.1055/s-0034-1380304

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Dichlorination of α-Diazo-β-dicarbonyls Using (Dichloroiodo)benzene

Authors

Keith E. Coffey

Department of Chemistry, University of Waterloo, 200 University Ave W., Waterloo, ON, N2L 3G1, Canada Email: graham.murphy@uwaterloo.ca
Graham K. Murphy*

Department of Chemistry, University of Waterloo, 200 University Ave W., Waterloo, ON, N2L 3G1, Canada Email: graham.murphy@uwaterloo.ca

Abstract

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Abstract

α-Diazo-β-dicarbonyl compounds were chlorinated using (dichloro)iodobenzene and an activating catalyst. A broad range of reaction rates was observed, which paralleled the relative stability/nucleophilicity of the diazo compounds. Acyclic diazocarbonyls reacted faster than cyclics, and β-diketones were much faster to react than β-keto esters or β-diesters. Lewis acid activation was used for the first time, allowing us to overcome instances of poor chemoselectivity. Though the yields ranged from low to good, this chlorination reaction has again proven a mild and effective halogenation strategy.

Key words

diazo compounds - hypervalent iodine - halogenation - catalysis - ylides

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References

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Supplementary Material

Supporting Information (PDF)