Shedding Light on the Diverse Reactivity of NacNacAl with N‐Heterocycles

The aluminum(I) compound NacNacAl (NacNac=ArNC(Me)CHC(Me)NAr]^?, Ar=2,6‐iPr₂C₆H₃, 1 ) shows diverse and substrate‐controlled reactivity in reactions with N‐heterocycles. 4‐Dimethylaminopyridine (DMAP), a basic substrate in which the 4‐position is blocked, induces rearrangement of NacNacAl by shifting a hydrogen atom from the methyl group of the NacNac backbone to the aluminum center. In contrast, C?H activation of the methyl group of 4‐picoline takes place to produce a species with a reactive terminal methylene. Reaction of 1 with 3,5‐lutidine results in the first example of an uncatalyzed, room‐temperature cleavage of an sp² C?H bond (in the 4‐position) by an Al^I species. Another reactivity mode was observed for quinoline, which undergoes 2,2′‐coupling. Finally, the reaction of 1 with phthalazine produces the product of N?N bond cleavage.