Skipped cyclic ene- and dienediynes. 1. Synthesis, spectroscopic properties, and reactions of a new hydrocarbon ring family

Article abstract of DOI:10.1021/ja00049a024

The three skipped cyclic C₁₂H₁₂ dienediynes, 4,9-dimethylene-1,6-cyclodecadiyne (1), (Z,Z)-4,10-cyclododecadiene-1,7-diyne (2), and 10-methylene-(Z)-4-cycloundecene-1,7-diyne (3), have been synthesized by cyclization of dilithium salts of diterminal enediynes with the corresponding dihalogenides. This simple approach only worked (with approx. 5% yield) when no CuCl catalyst was used. Besides 1-3, 4,9-diisopropylidene-1,6-cyclodecadiyne (30), the cyclic enediynes (Z)-4-cycloundecene-1,7-diyne (19) and (Z)-4-cyclododecene-1,7-diyne (20), as well as 4-methylene-1,6-cyclodecadiyne (22), 4-methylene-1,6-cycloundecadiyne (23), and their isopropylidene congeners 25 and 28 have been synthesized. Partial hydrogenation of 1-3 gives the corresponding homoconjugated tetraenes 37-39. The reaction of 30 with dicarbonyl(η⁵-cyclopentadienyl)cobalt yields a superphane of two cyclobutadiene units, stabilized by two CpCo moieties (47). The two cyclobutadiene rings are connected by four 2-isopropylidenepropano bridges. An X-ray investigation of the superphane shows that all four bridges adopt a pinwheel-like conformation.