Novel synthesis of 4,5-diarylphenanthrenes via C2-C6 cyclization of benzannulated enyne-allenes.
A new synthetic pathway to the 4,5-diarylphenanthrenes 8 having a helical twist in their structures was developed. The synthetic sequence involves condensation of the diketone 5 with 2 equiv of the lithium acetylides derived from the diacetylenes 4 followed by protonation to produce the propargylic alcohols 6. Reduction of 6 with triethylsilane in the presence of trifluoroacetic acid furnished the tetraacetylenic hydrocarbons 7 in nearly quantitative yields. Treatment of 7 with potassium tert-butoxide under refluxing toluene at 110 degrees C for up to 10 h then furnished the 4,5-diarylphenanthrenes 8. Apparently, the transformation from 7 to 8 involves initial prototropic isomerizations to form the benzannulated enyne-allenes 9. Two subsequent formal intramolecular Diels-Alder reactions via the biradicals 10 and 12 derived from the C(2)-C(6) cyclizations then led to 13, which in turn underwent tautomerizations to give 8. The structure of 8a was established by the X-ray structure analysis, showing that the two phenyl substituents are bent away from each other and the central aromatic system is severely distorted with a helical twist. The existence of a helical twist in 8 imposed by the aryl groups at the 4- and 5-positions was also revealed with a set of AB (1)H NMR signals for the diastereotopic methylene hydrogens on the five-membered rings.
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Department of Chemistry, West Virginia University, Morgantown, WV 26506-6045, USA.
Petersen
J L
JL
Wang
K K
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