Axially Chiral Stable Radicals: Resolution and Characterization of Blatter Radical Atropisomers

Atropisomers of three Blatter radicals were obtained by the addition of 8-substituted 1-naphthyllithiums to 3-phenyl and 3-t-butylbenzo[e][1,2,4]triazine and separated by chiral high-performance liquid chromatography. Their absolute configurations were assigned by a comparison of experimental and timedependent density functional theory calculated electronic circular dichroism spectra. The free energy of activation, Delta G(298)(double dagger), and the half life of racemization, t(1/2), at 298 K were determined at similar to 25 kcal mol(-1) and <130 h, respectively. Intramolecular pi-pi interactions in radicals were evident from single-crystal X-ray diffraction, density functional theory, and electrochemical analyses.

Automated summary

Three Atropisomers of Blatter radicals were synthesized and separated by chiral high-performance liquid chromatography. Their absolute configurations were determined through experimental and computational methods. Further analysis revealed the presence of intramolecular pi-pi interactions in the radicals.