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Updated: Jan 13, 2026

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes
Published on: April 1, 2013
1,2-Migratory ring expansion of a BN-naphthalene
Braden A Mediavilla1, Maxime A Siegler1, Rebekka S Klausen1
1Department of Chemistry, Johns Hopkins University, 3400 N Charles St, Baltimore, MD, USA. klausen@jhu.edu.
None:
Organoboranes hold an undeniable value in modern organic chemistry and show ever-growing potential in polymer design and functionalization. Azaborines, in particular, are still being explored as a promising class of organoboron compounds. We investigated the reactivity of a 1,2-azaborine towards Matteson homologation, a cornerstone of organoborane transformations. The azaborine was shown to be reactive towards nucleophiles. Addition of n-BuLi led to exchange of the R group, while addition of chloromethyllithium formed the desired tetracoordinate intermediate. However, rather than homologation, the complex readily underwent ring expansion via migration of the adjacent C(sp2), followed by deborylation. Computational analysis revealed a stable geometry of the azaboronate in which the migrating carbon is antiperiplanar to the leaving group, and which we propose as being responsible for the observed reactivity. This finding suggests a unique role for azaborines in molecular transformations which may be unachievable with other organoboron frameworks.
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