The aromatic Claisen rearrangement of a 1,2-azaborine.

ABSTRACT: 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 observ

SUBMITTER: Robichaud HM 

PROVIDER: S-EPMC10175209 | biostudies-literature | 2023 May

REPOSITORIES: biostudies-literature