Synthesis of Polyfunctionalized Bicyclo[5.3.1]undecadiene Ring Systems Using a Two‐Carbon Ring‐Expansion of Cyclobutene Intermediates

The ZrCl4-catalyzed [2+2] cycloaddition of the silyl enol ether derived from monoprotected bicyclo[3.3.1]nonane-2,6-dione 7 with ethyl propynoate led after acidic treatment to the cyclobutene derivative 12. Treatment of the latter with HBF4 in refluxing ethanol smoothly afforded the two-carbon ring-expansion product 13. On the other hand, the enolate of the β-oxobicyclo[3.3.1]nonane ester 14 has been found to react with electrophilic acetylenes [ethyl propynoate, dimethyl acetylenedicarboxylate (DMAD)] to afford bicyclo[5.3.1]undecadiene derivatives 15, 16, most probably through the intermediacy of a tricyclo[5.3.1.02,5]undecene ring system.

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