Cooperative activation of azides by an Al/N-based active Lewis pair – unexpected insertion of nitrogen atoms into C–Si bonds and formation of AlCN3 heterocycles

Abstract

Abstract The active Lewis pairs (ALPs) 2,6-Me2H8C5N–C(H) = C(SiMe3)–AlR2 (1a: R = t Bu, 1b, R = i Bu) have strained AlC2N heterocycles and relatively weak Al–N bonds. They react readily with a series of organic azides R′N3 [R′ = Ph, CH2C6H4(4- t Bu), t Bu, SiMe3, CH2Ph] by cleavage of the heterocycles and addition of the azides with their α-N atoms to the Al atom. The Al–N interactions result in an activation of the azide groups which insert into the C–Si bonds of the vinyl groups with their terminal γ-N atoms. Compounds with approximately planar five-membered AlCN3 heterocycles and intact N3 groups are formed in highly selective reactions.