Synthesis and conformational study of 1,1'-ethano-9,9'-bifluorenyl. Anti and Gauche conformers of a 9,9'-bifluorenyl derivative and chair and twist conformers of a dibenzo-1,5-cyclooctadiene derivative

Article abstract of DOI:10.1016/S0040-4020(01)86322-5

A Hofmann-type elimination of the sulphonium salt (18) under basic conditions led to the formation of a novel o-xylylene derivative (11) which dimerized regioselectively to give the bifluorenyl/dibenzo-1,5-cyclooctadiene derivative (3). The reaction is shown to be kinetically controlled and non-concerted. The two rigid conformers (3a) and (3b) were characterised by their ¹H NMR spectra and they represent respectively the first observed examples of an anti bifluorenyl derivative and a twist dibenzo-1,5-cyclooctadiene derivative. A semiempirical molecular orbital PM3 calculation supported the observed results. Dynamic ¹H NMR studies indicated an interconversion process (3a) ? (3b) at higher temperatures involving a conformational barrier estimated at 65.2 kJ mol^-1.