Preparation of 2-azaallyl anions and imines from N-chloroamines and their cycloaddition and allylation

Exposure of N-chloroamines to KOtBu or LDA, in the presence of PMDETA or HMPA, provides 2-azaallyl anions capable of π4s + π2s cycloaddition reactions with a range of olefins. Good yields were achieved with stabilised systems, however, they were more modest when accessing semi-stabilised 2-azaallyl anions. By modifying the reaction conditions, one-pot dehydrochlorination/allylation can also be achieved with a range of N-chloroamines.