Determination of the Rate Constant of the [4 + 2] Cycloaddition Between an Aryne Atropisomer and Furan in Solution

Guillaume Dauvergne (1) , Nicolas Vanthuyne (1) , Michel Giorgi (2) , Jean Rodriguez (1) , Yannick Carissan (1) , Yoann Coquerel (1)

1 ISM2 - Institut des Sciences Moléculaires de Marseille
2 FRSCM - Fédération des Sciences Chimiques de Marseille

Using a specially designed prototype of a nonracemic aryne atropisomer with a low barrier to enantiomerization (ca. 36 kJ•mol −1), it was possible to determine the kinetic constant of its cycloaddition with furan in solution by a combination of theoretical calculations and experimental measurements. It was found that the reaction half-life of this aryne atropisomer in solution with 100 equivalents of furan as the trapping reagent is <150 ns at temperatures above −20 °C. pubs.acs.org/joc Article

Keywords: Arynes; Atropisomer; Lifetime; Kinetic; Enantiomerization

Domains: Organic chemistry

Guillaume Dauvergne, Nicolas Vanthuyne, Michel Giorgi, Jean Rodriguez, Yannick Carissan, et al.. Determination of the Rate Constant of the [4 + 2] Cycloaddition Between an Aryne Atropisomer and Furan in Solution. Journal of Organic Chemistry, 2022, 87 (16), pp.11141 - 11147. ⟨10.1021/acs.joc.2c01394⟩. ⟨hal-03777717⟩