Cu(II)-Catalyzed ortho-Selective Aminomethylation of Phenols

A Cu­(II)-catalyzed ortho-selective functionalization of free phenols with trifluoroborates to afford Csp2–Csp3 coupling products under mild conditions has been developed. A variety of functional groups on the phenol and the potassium aminomethyltrifluoroborate substrates were found compatible, furn...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2017-09, Vol.139 (36), p.12390-12393
Main Authors: Dai, Jin-Ling, Shao, Nan-Qi, Zhang, Jin, Jia, Run-Ping, Wang, Dong-Hui
Format: Article
Language:English
Subjects:
Amines - chemistry
Catalysis
Copper - chemistry
Methylation
Phenols - chemistry
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Summary:A Cu­(II)-catalyzed ortho-selective functionalization of free phenols with trifluoroborates to afford Csp2–Csp3 coupling products under mild conditions has been developed. A variety of functional groups on the phenol and the potassium aminomethyltrifluoroborate substrates were found compatible, furnishing the corresponding products in moderate to excellent yields. A single-electron transfer radical coupling mechanism involving a six-membered transition state is proposed to rationalize the high levels of ortho-selectivity in the reaction. This protocol provides straightforward access to ortho-aminomethyl-substituted phenols, unnatural amino acids and other bioactive small molecules.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.7b06785