N-phosphino- and N-phosphonionitrilimines: from nucleophilic to electrophilic 1,3-dipoles

摘要

N[Bis(diisopropylamino)phosphino]-C[bis(diisopropylamino)thioxophosphoranyl]nitrlilimine (1)re- acts with electron-poor dipolarophilesw such as maleimide, methyl vinyl ketone, and 1,4-naphtho- qunone via HOMO(dipole)-controlled [2+3] cycloadditions, cycloaddition, ehile N-[bis(diisopropylamino)(methyl)- phosphonio-]-C-[bis(diisopropylamino)thixosphosphoranyl]nitrilimine (2a) reacts with electron-rich dipolarophiles such as norbornadiene and ethyl trans-pyrrolineacrylate via LUMO(dipole)-controlled [2+3] cycloadditions.