ol6b02417_si_001.pdf (10.37 MB)
Ring Expansion of Donor–Acceptor Cyclopropane via Substituent Controlled Selective N‑Transfer of Oxaziridine: Synthetic and Mechanistic Insights
journal contribution
posted on 2016-09-29, 13:26 authored by Asit Ghosh, Subhajit Mandal, Pratim Kumar Chattaraj, Prabal BanerjeeA distinctive N-substituent controlled electrophilic N-transfer of oxaziridines with donor–acceptor cyclopropanes
in the presence of MgI2 is reported. Contrary to earlier
reports, the oxaziridine having bulkier N-substituents
can also give N-transferred product instead of the O-transferred one. Interestingly, the oxaziridines having
α-H containing N-substituents lead to the pyrrolidine
derivatives through [3 + 2] cycloaddition. A mechanistic reasoning
for this divergent reactivity is depicted by density functional theory
calculations and validated through energy decomposition analysis.