Cobalt-Catalyzed [2+2+2] Cycloaddition of Phenylacetylene with 1,3-Dienes for the Synthesis of Vinyl-Substituted 1,4-Diphenylcyclohexa-1,3-dienes

Abstract

The cobalt-catalyzed [2+2+2] cycloaddition of two alkynes and a 1,3-diene, utilizing either a dibromo[1,2-bis(diphen­ylphosphino)]benzene cobalt or a dibromobis(triphenylphosphino)cobalt complex, under reductive conditions gives vinyl-substituted cyclohexa-1,3-diene derivatives in acceptable yields. The oxidation of 5-methyl-1,4-diphenyl-5-vinylcyclohexa-1,3-diene by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone leads to a rearrangement resulting in a vinyl-terphenyl derivative.

cobalt - cycloaddition - cyclohexadiene - oxidation

References

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The ratios were determined by GC/GCMS analysis. The missing percentages result from unidentified side products.

<A NAME="RZ23407SS-10">10</A>

CCDC 659433 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

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The quality of the crystal was significantly reduced by disordered solvent within the crystal cell.

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The R _f values of TLC analysis utilizing pentane as the eluent span a range between 0.75 and 0.90.

<A NAME="RZ23407SS-15">15</A>

¹H NMR data were assigned of the major component to the best of our knowledge and ¹³C NMR and HRMS data were not obtained based on the low purity of the sample.