Korth Hans-Gert, Mulder Peter, Paul Thomas
Institut für Organische Chemie, Universität Duisburg-Essen, 45117 Essen, Germany.
Leiden Institute of Chemistry, Leiden University, 2300 RA Leiden, The Netherlands.
Phys Chem Chem Phys. 2017 Jan 25;19(4):3405-3408. doi: 10.1039/c6cp04187f.
Despite the claim of the contrary, (i) the facile formation of a ring-opened cyclic peroxide from reaction of a 1,2-disubstituted benzocyclobutene with molecular oxygen has been reported before, and (ii) the analysis of the mechanistic steps of this process is incomplete, as only the symmetry-allowed conrotatory ring-opening of the benzocyclobutene has been considered. The probable involvement of biradical intermediates/biradicaloid transition states in a formally symmetry-forbidden reaction sequence has not been taken into account.
尽管有相反的说法,但(i)之前已有报道称1,2-二取代苯并环丁烯与分子氧反应能轻易形成开环环状过氧化物,且(ii)该过程的机理步骤分析并不完整,因为仅考虑了苯并环丁烯的对称允许的顺旋开环。尚未考虑在形式上对称禁阻的反应序列中双自由基中间体/类双自由基过渡态可能的参与情况。