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1.4.1.8.4 Inter- and Intramolecular [2+2+2] Cyclization of Diynes with Heteroatom-Substituted Multiple Bonds

DOI: 10.1055/sos-SD-001-00322

Malacria, M.; Aubert, C.; Renaud, J.-L.Science of Synthesis, (20011458.

Cyclopentadienone complexes may be obtained not only by carbonylation of isolated metallacyclopentadienes but directly from the intermolecular reaction of two alkynes and dicarbonyl(η5-cyclopentadienyl)cobalt(I) (1). It has been found that trimethylsilylalkynes or alkynes bearing polar electron-withdrawing substituents undergo such reactions under low-temperature photolytic conditions in the presence of stoichiometric amounts of 1 to furnish complexed cyclopentadienones with good regioselectivity.[‌95‌] For example, complex 48 was the major product in the cyclization of trimethylsilylacetylene with 1 (Scheme 25), whereas the corresponding 2,4-disilylated product 49 predominated when dicarbonyl(η5-pentamethylcyclopentadienyl)cobalt(I) was employed.

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