Cine substitution in 2-oxabicyclo[4.2.0]octanones and subsequent unusual rearrangements

Alfred Hassner, Simha Naidorf-Meir, Aryeh A. Frimer

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12 Scopus citations


Reaction of 2-chlorooxabicyclo[4.2.0]octanone 5 with several nucleophiles was examined and found to differ significantly from those of carbon analog 1. MeO- and PhS- led either to products of cine substitution 9 or of ring opening to cyclobutenones 8. With most enolates cine substitution occured via C-alkylation of the intermediate oxidoallyl cation in spite of formation of a new C-C bond between two quaternary carbons; with nitroalkanes O-alkylation was preferred. With azide as a nucleophile, further transformations occurred, among them an oxy-promoted electrocyclic cyclobutane opening, with incorporation of a phenyl triazole unit and final formation of the unusual product 19a. Evidence for a mechanism explaining formation of 19a was obtained by isolation of intermediates. Thermolysis or photolysis of 8e or 9b led via electrocyclic ring opening to a vinyl ketene which was trapped by MeOH, alkenes, dienes, or oxygen to produce polyfunctional unsaturated esters 29 and 30 or 8-membered ring lactone 31, fused cyclobutanones 33 and 34, pyranone 38, or γ-lactone 39, respectively.

Original languageEnglish
Pages (from-to)4051-4058
Number of pages8
JournalJournal of Organic Chemistry
Issue number12
StatePublished - 14 Jun 1996


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