Shedding Light on the Diverse Reactivity of NacNacAl with N-Heterocycles |
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| Authors: | Anton Dmitrienko Prof. Melanie Pilkington Dr. James F. Britten Dr. Bulat M. Gabidullin Prof. Art van der Est Prof. Georgii I. Nikonov |
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| Affiliation: | 1. Chemistry Department, Brock University, 1812 Sir Isaac Brock Way, St. Catharines, Ontario, L2S 3A1 Canada;2. Department of Chemistry & Biology, McMaster University, 1280 Main Street West, Hamilton, Ontario, L8S 4L8 Canada;3. X-Ray Core Facility, University of Ottawa, 150 Louis Pasteur, Ottawa, Ontario, K1N 6N5 Canada |
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| Abstract: | 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 AlI 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. |
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| Keywords: | aluminum C−C coupling C−H activation N-heterocycles reductive coupling |
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