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An all-purpose preparation of oxime carbonates and resultant insights into the chemistry of alkoxycarbonyloxyl radicals

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Roy Thomas McBurney, Andrew D. Harper, Alexandra Martha Zoya Slawin, John Christopher Walton

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Abstract

Oxime carbonates have been synthesised and their potential studied as a new class of radical precursor. A general synthetic route, avoiding laboratory use of phosgene, was developed. Alkyl or aryl 1H-imidazole-1-carboxylates were prepared from the corresponding alcohols and 1,1-carbonyldiimidazole, then reacted with oximes in the presence of base. UV photolyses of oxime carbonates released particular N- and O-centred radicals suitable for spectroscopic examination. Spiro-cyclisations of alkoxycarbonyloxyl radicals onto aromatic acceptors and 5-exo cyclisations onto alkene acceptors were studied by EPR spectroscopy. EPR data also provided insight to the loss of CO2 from alkoxycarbonyloxyl radicals. The conformational preferences of 2-oxo-1,3-dioxolan-4-yl-methyl and related radicals were established. Modest yields of cyclic carbonates were obtained from preparative scale photolyses.

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Original languageEnglish
Pages (from-to)3436-3444
Number of pages9
JournalChemical Science
Volume3
Issue number12
DOIs
StatePublished - Dec 2012

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