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- Title
Photochemical Intramolecular C−H Addition of Dimesityl(hetero)arylboranes through a [1,6]-Sigmatropic Rearrangement.
- Authors
Ando, Naoki; Fukazawa, Aiko; Kushida, Tomokatsu; Shiota, Yoshihito; Itoyama, Shuhei; Yoshizawa, Kazunari; Matsui, Yasunori; Kuramoto, Yutaro; Ikeda, Hiroshi; Yamaguchi, Shigehiro
- Abstract
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 π-conjugation, the resulting spirocyclic boraindanes exhibited a characteristic absorption band at relatively long wavelengths ( λ=370-400 nm).
- Subjects
PERICYCLIC reactions; ORGANOBORON compounds; ORGANIC compounds; BORON; PHOTOCHEMICAL kinetics
- Publication
Angewandte Chemie, 2017, Vol 129, Issue 40, p12378
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201706929