Amination of Aryl Chlorides via Benzynes Catalyzed by Sodium Alkoxide Clusters

Contributor(s):

Yasuhiro Uozumi

Kenji Tsukamoto

Yao J. -L, Zhang Z, Li Z. * ShanghaiTech University, P. R. of China
Scalable Transition-Metal-Free Synthesis of Aryl Amines from Aryl Chlorides through X@RONa-Catalyzed Benzyne Formation.

J. Am. Chem. Soc. 2024;
146: 8839-8846
DOI: 10.1021/jacs.4c00426.

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Key words

aryl amines - aryl chlorides - benzynes - sodium alkoxide cluster

Significance

Amination of aryl chlorides took place with NaH in the presence of catalytic 1-methoxy-2-methylpropan-2-ol and N-ethylimidazole at 80 °C to give aryl amines (60 examples) via the corresponding benzynes in up to 98% yield (eq. 1). A molar scale reaction of 4-methylpiperidine (0.5 mol) with PhCl was performed to afford 4-methyl-1-phenylpiperidine in 80% yield (86.5 g).

Comment

In this reaction, PhCl showed superior reactivity over PhF, PhBr, and PhI. ArCls with ortho or meta substituents provided meta-aminated products with high regioselectivity. The authors discovered that sodium tertiary alkoxides assemble to form dodecameric truncated octahedral clusters which dissolve NaH to promote the benzyne formation from aryl chlorides.

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Publication History

Article published online:
14 June 2024

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

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