Nickel-catalysed direct alkylation of thiophenes via double C(sp3)–H/C(sp2)–H bond cleavage: the importance of KH2PO4

Xie Wang; Peipei Xie; Renhua Qiu; Longzhi Zhu; Ting Liu; You Li; Takanori Iwasaki; Chak-Tong Au; Xinhua Xu; Yuanzhi Xia; Shuang-Feng Yin; Nobuaki Kambe

doi:10.1039/C7CC04252C

Nickel-catalysed direct alkylation of thiophenes via double C(sp³)–H/C(sp²)–H bond cleavage: the importance of KH₂PO₄†

Xie Wang,‡^a Peipei Xie,‡^b Renhua Qiu,

*^ac Longzhi Zhu,

^ac Ting Liu,^a You Li,^a Takanori Iwasaki,

^c Chak-Tong Au,^ad Xinhua Xu,

^a Yuanzhi Xia,

*^b Shuang-Feng Yin

*^a and Nobuaki Kambe^c

Author affiliations

* Corresponding authors

^a State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, China
E-mail: renhuaqiu@hnu.edu.cn, sf_yin@hnu.edu.cn

^b College of Chemistry and Chemical Engineering, Wenzhou University, Wenzhou, P. R. China
E-mail: xyz@wzu.edu.cn

^c Graduate School of Engineering, Osaka University, Suita, Osaka, Japan

^d College of Chemistry and Chemical Engineering, Hunan Institute of Engineering, Xiangtan, P. R. China

Abstract

A Ni-catalyzed oxidative C–H/C–H cross-dehydrogenative coupling (CDC) reaction was developed for constructing various highly functionalized alkyl (aryl)-substituted thiophenes. This method employs thiophenes and aliphatic (aromatic) amides that contain an 8-aminoquinoline as a removable directing group in the presence of a silver oxidant. The approach enables the facile one-step synthesis of substituted thiophenes with high functional group compatibility via double C–H bond cleavage without affecting C–Br and C–I bonds. DFT calculations verify the importance of KH₂PO₄ as an additive for promoting C–H bond cleavage and support the involvement of a Ni(III) species in the reaction.

Chemical Communications

Nickel-catalysed direct alkylation of thiophenes via double C(sp³)–H/C(sp²)–H bond cleavage: the importance of KH₂PO₄†

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Nickel-catalysed direct alkylation of thiophenes via double C(sp³)–H/C(sp²)–H bond cleavage: the importance of KH₂PO₄

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