Details

Autor(en) / Beteiligte

• Dmitrienko, Anton
• Pilkington, Melanie
• Britten, James F.
• Gabidullin, Bulat M.
• Est, Art
• Nikonov, Georgii I.

Titel

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

Ist Teil von

• Angewandte Chemie International Edition, 2020-09, Vol.59 (37), p.16147-16153

Auflage

International ed. in English

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2020

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• 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. Reactivity pathways of NacNacAl with various N‐heterocycles have been investigated and diverse and highly substrate‐controlled reactivity patterns have been discovered. Cases of unusual sp3 and sp2 C−H bond activation, C−C coupling, and N−N bond cleavage are reported. NacNac=[ArNC(Me)CHC(Me)NAr]−, Ar=2,6‐iPr2C6H3.