Wet carbonate-promoted radical arylation of vinyl pinacolboronates with diaryliodonium salts yields substituted olefins

Chao Wu; Chongyang Zhao; Jun Zhou; Han-Shi Hu; Jun Li; Panpan Wu; Chao Chen

doi:10.1038/s42004-020-00343-8

Wet carbonate-promoted radical arylation of vinyl pinacolboronates with diaryliodonium salts yields substituted olefins

Commun Chem. 2020 Jul 22;3(1):92. doi: 10.1038/s42004-020-00343-8.

Authors

Chao Wu^#¹, Chongyang Zhao^#², Jun Zhou^{3

4}, Han-Shi Hu⁵, Jun Li², Panpan Wu^{3

4}, Chao Chen^{6

7

8}

Affiliations

¹ Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology (Ministry of Education), Department of Chemistry, and the Graduate School at Shenzhen, Tsinghua University, 100084, Beijing, China.
² Department of Chemistry & Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education, Tsinghua University, 100084, Beijing, China.
³ Environmental Engineering, Wuyi University, Jiangmen, 529000, China.
⁴ International Healthcare Innovation Institute (Jiangmen), Jiangmen, 529000, China.
⁵ Department of Chemistry & Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education, Tsinghua University, 100084, Beijing, China. hshu@mail.tsinghua.edu.cn.
⁶ Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology (Ministry of Education), Department of Chemistry, and the Graduate School at Shenzhen, Tsinghua University, 100084, Beijing, China. chenchao01@mails.tsinghua.edu.cn.
⁷ Environmental Engineering, Wuyi University, Jiangmen, 529000, China. chenchao01@mails.tsinghua.edu.cn.
⁸ International Healthcare Innovation Institute (Jiangmen), Jiangmen, 529000, China. chenchao01@mails.tsinghua.edu.cn.

^# Contributed equally.

Abstract

Since the landmark work of Heck, Negishi and Suzuki on Pd-catalyzed crossing coupling reactions, innovative discovery of new reactions forming C-C bonds and constructing functional olefins via nonmetal catalysts remains an imperative area in organic chemistry. Herein, we report a transition-metal-free arylation method of vinyl pinacolboronates with diaryliodonium salts to form C(sp²)-C(sp²) bond and provide trans-arylvinylboronates. The resulting vinylboronates can further react with the remaining aryl iodides (generated from diaryliodonium salts) via Suzuki coupling to afford functional olefins, offering an efficient use of aryliodonium salts. Computational mechanistic studies suggest radical-pair pathway of the diaryliodonium salts promoted by the multi-functional wet carbonate.

Abstract

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