Ring Expansion of Donor-Acceptor Cyclopropane via Substituent Controlled Selective N-Transfer of Oxaziridine: Synthetic and Mechanistic Insights.
A distinctive N-substituent controlled electrophilic N-transfer of oxaziridines with donor-acceptor cyclopropanes in the presence of MgI2is 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.
Department of Chemistry, Indian Institute of Technology Ropar , Nangal Road, Rupnagar, Punjab 140001, India.
Asit
A
Ghosh
Department of Chemistry, Indian Institute of Technology Kharagpur , Kharagpur, West Bengal 721302, India.
Subhajit
S
Mandal
Department of Chemistry, Indian Institute of Technology Kharagpur , Kharagpur, West Bengal 721302, India.
Pratim Kumar
PK
Chattaraj
Department of Chemistry, Indian Institute of Technology Ropar , Nangal Road, Rupnagar, Punjab 140001, India.
Prabal
P
Banerjee