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Synfacts 2022; 18(04): 0385
DOI: 10.1055/s-0041-1737962
Metals in Synthesis

The Direct Coupling of Phenols and Amines under Rhodium Catalysis

Contributor(s):
Martin Oestreich
,
Hendrik F. T. Klare
,
Lucie Finck
Chen K, Kang Q.-K, Li Y, Wu W.-Q, Zhu H, Shi H. * Westlake University and Westlake Institute for Advanced Study, Hangzhou, P. R. of China
Catalytic Amination of Phenols with Amines.

J. Am. Chem. Soc. 2022;
144: 1144-1151
DOI: 10.1021/jacs.1c12622.
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Key words

amines - anilines - cross-coupling - phenols - rhodium catalysis

Significance

A redox-neutral strategy for the dehydrative coupling of phenols and amines enabled by a dimeric cyclopentadienyl rhodium(III) complex is disclosed. The reaction proceeds under mild conditions, releasing water as the sole by-product. This method is also applicable to late-stage functionalization.


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Comment

Starting from readily available primary or secondary amines and phenols, this transformation provides access to a wide range of valuable anilines in good yields. Mechanistic experiments support a keto–enol tautomerization of phenol as the key step, facilitated by η6-coordination of the aryl ring by the rhodium complex.


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Publication History

Article published online:
18 March 2022

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