Shedding Light on the Diverse Reactivity of NacNacAl with N‐Heterocycles
Anton Dmitrienko, Melanie Pilkington, James F. Britten, Bulat Gabidullin, Art van der Est, Georgii I. Nikonov
Abstract
Abstract The aluminum(I) compound NacNacAl (NacNac=[ArNC(Me)CHC(Me)NAr] − , Ar=2,6‐ i Pr 2 C 6 H 3 , 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 sp 2 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.