Nitrous Oxide-Promoted Pauson-Khand Cycloadditions

A Pauson-Khand cycladdition of alkynes, alkenes, and carbon monoxide, promoted by cobalt carbonyl and nitrous oxide to furnish cyclopentenones is described. Preliminary mechanistic experiments suggest that nitrous oxide functions in a similar manner to the N-oxide promoters typically employed in Pauson-Khand reactions. Only dinitrogen and carbon dioxide are produced as a consequence of the activation mechanism, thus avoiding high molecular weight reagents and the build up of basic byproducts. The chemistry is done using equimolar amounts of alkyne, alkene, and dicobalt octacarbonyl, and is performed directly from the acetylenic component without having to presynthesize a cobalt-alkyne complex. Terminal acetylenes were suitable substrates, as was solid calcium carbide, and the corresponding adducts were isolated in good yields. Furthermore, two sequential [4+3] and [2+2+1] cycloadditions were performed, generating funtionalized cyclopentenones in only two steps from readily available starting materials.