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Shedding Light on the Diverse Reactivity of NacNacAl with N‐Heterocycles
Author(s) -
Dmitrienko Anton,
Pilkington Melanie,
Britten James F.,
Gabidullin Bulat M.,
Est Art,
Nikonov Georgii I.
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202005925
Subject(s) - chemistry , reactivity (psychology) , quinoline , cleavage (geology) , stereochemistry , methyl group , medicinal chemistry , methylene , bond cleavage , substrate (aquarium) , photochemistry , group (periodic table) , organic chemistry , catalysis , materials science , medicine , alternative medicine , oceanography , pathology , fracture (geology) , geology , composite material
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.