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
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.
