Synthesis 2022; 54(18): 4025-4032
DOI: 10.1055/a-1838-8958
paper

Bromide as the Directing Group for β-Arylation of Thiophenes

Cai-Xia Wang
a   Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Jiangsu National Synergistic Innovation Center for Advanced Materials (SICAM), Nanjing Tech. University (Nanjing Tech.), 30 Puzhu Road, Nanjing 211816, P. R. of China
,
Fei-Fei Sheng
a   Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Jiangsu National Synergistic Innovation Center for Advanced Materials (SICAM), Nanjing Tech. University (Nanjing Tech.), 30 Puzhu Road, Nanjing 211816, P. R. of China
,
Kai-Hui Liu
a   Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Jiangsu National Synergistic Innovation Center for Advanced Materials (SICAM), Nanjing Tech. University (Nanjing Tech.), 30 Puzhu Road, Nanjing 211816, P. R. of China
,
Jian-Guo Gu
a   Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Jiangsu National Synergistic Innovation Center for Advanced Materials (SICAM), Nanjing Tech. University (Nanjing Tech.), 30 Puzhu Road, Nanjing 211816, P. R. of China
,
Kang Shen
a   Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Jiangsu National Synergistic Innovation Center for Advanced Materials (SICAM), Nanjing Tech. University (Nanjing Tech.), 30 Puzhu Road, Nanjing 211816, P. R. of China
,
Zheng-Yi Sun
a   Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Jiangsu National Synergistic Innovation Center for Advanced Materials (SICAM), Nanjing Tech. University (Nanjing Tech.), 30 Puzhu Road, Nanjing 211816, P. R. of China
,
Kunlun Hong
b   Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA
,
a   Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Jiangsu National Synergistic Innovation Center for Advanced Materials (SICAM), Nanjing Tech. University (Nanjing Tech.), 30 Puzhu Road, Nanjing 211816, P. R. of China
› Institutsangaben
We acknowledge funding from the National Natural Science Foundation of China.


Abstract

Direct β-arylation of thiophene derivatives with bromide as directing group is disclosed. The reaction is conducted with PdCl2/(p-tolyl)3P as catalyst, silver carbonate as additive, and aryl iodide as coupling partner, affording brominated biaryl compounds as product. Control experiments indicated that the presence of bromide group enhances the reactivity of the C–H bond, enabling β-arylation. Furthermore, the C–Br bond can be easily converted into many useful functional groups through a wide range of methodologies. The mechanistic study suggests that silver salt plays a key role in the C–H bond-activation step.

Supporting Information



Publikationsverlauf

Eingereicht: 18. März 2022

Angenommen nach Revision: 28. April 2022

Accepted Manuscript online:
28. April 2022

Artikel online veröffentlicht:
28. Juni 2022

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