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- Title
Selective Cross‐Coupling of Unsaturated Substrates on Al<sup>I</sup>.
- Authors
Dmitrienko, Anton; Pilkington, Melanie; Nikonov, Georgii I.
- Abstract
The AlI compound NacNacAl (1, NacNac = [ArNC(Me)CHC(Me)NAr]−, Ar = 2,6‐iPr2C6H3) serves as a template for the chemoselective coupling between carbonyls (benzophenone, fenchone, isophorone, p‐tolyl benzoate, N,N‐dimethylbenzamide, (1‐phenylethylidene)aniline) and pyridine. With the CH‐acidic ketone (1R)‐(+) camphor, the reaction affords a hydrido alkoxide compound of Al, formed as the result of enolization, whereas an enolizable imine, (1‐phenylethylidene)aniline, and the bulky ketone isophorone, still chemoselectively couple with pyridine. In contrast, reaction with the ester p‐tolyl benzoate results in cleavage of the ester bond together with replacement of the alkoxy group by a hydrogen atom of the pyridine moiety. This study demonstrates that for carbonyl substrates featuring phenyl substituents, the reaction proceeds via intermediate formation of η2(C,X)‐coordinated (X = O, N) carbonyl adducts, whereas the reaction of 1 with (R)‐(−)‐fenchone in the absence of pyridine leads to CH activation in the pendant isopropyl group of the Ar substituent of the NacNac ligand.
- Subjects
ALKOXY group; HYDROGEN atom; BENZOATES; ISOPHORONE; CAMPHOR; ENOLIZATION; HYDROXYBENZOPHENONES
- Publication
Chemistry - A European Journal, 2021, Vol 27, Issue 18, p5730
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202004907