Biradicals from benzoenyne-allenes. Application in the synthesis of 11H-benzo[b]fluoren-11-ols, 1H-cyclobut[a]indenes, and related compounds.

New synthetic pathways to 11H-benzo[b]fluoren-11-ols, 1H-cyclobut[a]indenes, and related compounds via biradicals generated from benzoenyne-allenes were developed. Treatment of the diacetylenic propargylic alcohols 13, derived from condensation between benzophenones and the lithium acetylide of 1-(2-ethynylphenyl)-2-phenylethyne, with thionyl chloride produced the 11-chloro-11H-benzo[b]fluorene 14 and, after hydrolysis, the corresponding 11H-benzo[b]fluoren-11-ols 15. The transformation involved a sequence of reactions, including a biradical-forming C2-C6 cyclization (Schmittel cyclization) reaction of the chlorinated benzoenyne-allene intermediates followed by an intramolecular radical-radical coupling to form the formal Diels-Alder adducts. Interestingly, in the case of the diacetylenic propargylic alcohol 26, obtained from dibenzosuberenone (25), an intramolecular [2 + 2] cycloaddition reaction of the chlorinated benzoenyne-allene intermediate occurred, furnishing the 1H-cyclobut[a]indene 27 exclusively. The dramatic change of the reaction pathway could be attributed to the emergence of a steric strain due to the nonbonded interactions with the chloro substituent along the pathway toward the formal Diels-Alder adduct 31. On the other hand, the non-chlorinated benzoenyne-allene, derived from prototropic isomerization of the diacetylenic hydrocarbon 60, underwent a formal Diels-Alder reaction to furnish the 11H-benzo[b]fluorene-type hydrocarbon 61 exclusively.