Peng Qin, Cui‐Wu Lin, H Li, Mi Zhou, Nan Huang, Jun Jiang
An efficient, strain-driven ring opening of 3-alkylideneazetidines has been developed, enabling the one-step construction of both carbon–halogen and carbon–nitrogen bonds to afford structurally diverse β-halomethyl allylamines.
An efficient, strain-driven ring opening of 3-alkylideneazetidines has been developed, enabling the one-step construction of both carbon–halogen and carbon–nitrogen bonds to afford structurally diverse β-halomethyl allylamines. This transformation is initiated by arynes as electrophiles, forming an azetidinium intermediate that undergoes nucleophilic attack by a halide anion to proceed with the ring-opening reaction. The protocol features the advantages of inexpensive and environmentally benign potassium halides as halogen sources, transition-metal-free conditions, and high stereoselectivity ( E / Z ). The utility of the resulting β-halomethyl allylamines was demonstrated by their further transformation into valuable allylamines and potential anti-inflammatory activity in preliminary bioassays.