Photochemical Intramolecular C-H Addition of Dimesityl(hetero)arylboranes through a [1,6]-Sigmatropic Rearrangement

A new reaction mode for triarylboranes under photochemical conditions was discovered. Photoirradiation of dimesitylboryl-substituted (hetero)arenes produced spirocyclic boraindanes, where one of the C-H bonds in the ortho-methyl groups of the mesityl substituents was formally added in a syn fashion to a C-C double bond of the (hetero)aryl group. Quantum chemical calculations and laser flash photolysis measurements indicated that the reaction proceeds through a [1,6]-sigmatropic rearrangement. This behavior is reminiscent of the photochemical reaction mode of arylalkenylketones, thus demonstrating the isosteric relation between tricoordinate organoboron compounds and the corresponding pseudo-carbocationic species in terms of pericyclic reactions. Despite the disrupted -conjugation, the resulting spirocyclic boraindanes exhibited a characteristic absorption band at relatively long wavelengths (=370400 nm).