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Journal Articles Organic & Biomolecular Chemistry Year : 2023

The aromatic Claisen rearrangement of a 1,2-azaborine


The first aromatic Claisen rearrangement of a 1,2-azaborine is described along with a quantitative kinetic comparison of the reaction of the azaborine with its direct all-carbon analogue. The azaborine A rearranged in a clean, regioselective fashion and reacted faster than the all-carbon substrate B at all temperatures from 140-180 °C. Activation free energies were extracted from observed first-order rate constants (A: ΔG‡298K = 32.7 kcal mol−1; B: ΔG‡298K = 34.8 kcal mol−1) corresponding to a twenty fold faster rate for A at observed reaction temperatures. DFT calculations show that the rearrangement proceeds via a concerted six-membered transition state and that the electronic structure of the BN and CC rings is mostly responsible for the observed regioselectivity and relative reactivity.
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Dates and versions

hal-04094407 , version 1 (27-07-2023)



Hannah Robichaud, Jacob Ishibashi, Tomoya Ozaki, Walid Lamine, Karinne Miqueu, et al.. The aromatic Claisen rearrangement of a 1,2-azaborine. Organic & Biomolecular Chemistry, 2023, 21 (18), pp.3778-3783. ⟨10.1039/d2ob02186b⟩. ⟨hal-04094407⟩
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