Impact of Transition-State Aromaticity on Selective Radical–Radical Coupling of Triarylimidazolyl Radicals

Radical coupling reactions are generally known to have a low selectivity due to the high reactivity of radicals. In this study, high regio and substrate selectivity was discovered in the dimerization of triarylimidazolyl radicals (<b>TAIR</b>), a versatile photochromic reaction. When two different radicals, 2-(4-cyanophenyl)-4,5-diphenyl-1<i>H</i>-imidazolyl radical (<b>CN-TAIR</b>) and 2-(4-methoxyphenyl)-4,5-diphenyl-1<i>H</i>-imidazolyl radical (<b>OMe-TAIR</b>), were simultaneously generated in situ, a hexaarylbiimidazole, formed by selective coupling at the nitrogen atom at position 1 of <b>CN-TAIR</b> and the carbon atom at position 2 of <b>OMe-TAIR</b>, was isolated with high selectivity as the main product among 24 possible radical dimer hexaarylbiimidazole derivatives. This high regio and substrate selectivity cannot be explained solely by the stability of the product and/or the electrophilicity and nucleophilicity of the radicals but originates from the aromaticity of the transition state in the radical-radical coupling reaction. To date, the selectivity of radical coupling reactions has been thought to be controlled by steric hindrance and radical spin density, but this study revealed a new factor for controlling radical coupling, that is, transition-state aromaticity. Aromaticity has been reported to have an important effect not only in the reactivity and structure of ground-state molecules but also on the electronically excited states and transition states in pericyclic reactions such as the Diels-Alder reaction and the Cope-Claisen rearrangement. This study demonstrated for the first time that radical coupling reactions can also be controlled by transition-state aromaticity.