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Synthesis 2022; 54(02): 403-410
DOI: 10.1055/a-1587-8859
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Palladium-Catalyzed Butoxycarbonylation of Polybromo(hetero)arenes: A Practical Method for the Preparation of (Hetero)arenepolycarboxylates and -carboxylic Acids

Weilong Wu
a   College of Chemistry and Chemical Engineering and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang, 471934, P. R. of China
,
Yongkang Jing
a   College of Chemistry and Chemical Engineering and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang, 471934, P. R. of China
,
Deyi Zhang
b   College of Chemistry, Zhengzhou University, Zhengzhou, Henan 450001, P. R. of China
,
Xianghe Yan
a   College of Chemistry and Chemical Engineering and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang, 471934, P. R. of China
,
Rong Liang
c   College of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, P. R. of China
,
Zhiqiang Lu
a   College of Chemistry and Chemical Engineering and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang, 471934, P. R. of China
,
Baoming Ji  ∗
a   College of Chemistry and Chemical Engineering and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang, 471934, P. R. of China
› Author AffiliationsThis work was supported by the National Natural Science Foundation of China (21372112 and 21801112), the Key Scientific Research Project of Colleges and Universities in Henan Province (19A150004), the General Science Foundation of Henan Province of China (212300410374), and Cultivation Fund of Luoyang Normal University.
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Abstract

The palladium-catalyzed alkoxycarbonylation of polybromo­(hetero)arenes was investigated systematically. The results show that cheap and readily available in situ Pd(OAc)2/rac-BINAP catalyst can catalyze the butoxycarbonylation of various polybromo(hetero)arenes efficiently, and gave (hetero)arenepolycarboxylates with moderate to high yield (59–94%). Using this method, two new compounds, 4,4′-bis(butoxycarbonyl)-1,1′-bi-2-naphthol and dibutyl [2,2′-bipyrimidine]-5,5′-dicarboxylate, are reported for the first time. In addition, the gram-scale preparation of carboxylate and carboxylic acids was successful performed by butoxycarbonylation followed by hydrolysis. This shows the wide scope of substrates and practical applications of the Pd(OAc)2/rac-BINAP catalytic system. Moreover, these carboxylic acids and carboxylates can be used as ligands or structural units to construct MOFs, metal complexes, and COFs etc.

Key words

polybromoarenes - polybromoheteroarenes - butoxycarbonylation - palladium catalyst - polycarboxylic acid - ligand

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1587-8859.
  • Supporting Information

Primary Data

    Primary data for this article are available online at ­https://zenodo.org/record/5179843 and can be cited using the following DOI: 10.5281/zenodo.5179843.



Publication History

Received: 07 July 2021

Accepted after revision: 16 August 2021

Accepted Manuscript online:
16 August 2021

Article published online:
30 September 2021

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