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Nickel-Catalyzed Cross-Electrophile C(sp3)-Si Coupling of Unactivated Alkyl Bromides with Vinyl Chlorosilanes

Jicheng Duan, Yuquan Wang, Liangliang Qi, Peng Guo, Xiaobo Pang and Xing-Zhong Shu*

*State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou 730000, China, Email: shuxingzhlzu.edu.cn

J. Duan, Y. Wang, L. Qi, P. Guo, X. Pang, X.-Z. Shu, Org. Lett., 2021, 23, 7855-7859.

DOI: 10.1021/acs.orglett.1c02874


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Abstract

A C(sp3)-Si coupling of unactivated alkyl bromides with vinyl chlorosilanes proceeds under mild conditions to provide alkylsilanes. Functionalities such as Grignard-sensitive groups (e.g., acid, amide, alcohol, ketone, and ester), acid-sensitive groups (e.g., ketal and THP protection), alkyl fluoride and chloride, aryl bromide, alkyl tosylate and mesylate, silyl ether, and amine were tolerated.

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proposed mechanism



Ni-catalyzed cross-electrophile C-Si coupling of alkyl bromides with vinyl chlorosilanes

The procedure was conducted in an argon-filled glove box. To a reaction tube equipped with a magnetic stir bar was added NiCl2 (2.6 mg, 0.02 mmol), 2,9-di-sbu-phen (5.8 mg, 0.02 mmol), and Mn (22.0 mg, 0.4 mmol). A solution of alkyl bromide (0.2 mmol) and chlorosilane (0.2 mmol) in DMF (1.0 mL) was then added. The reaction tube was sealed and removed from the glove box. The reaction mixture was stirred at 0 °C for 24 h. The reaction was quenched with water (20.0 mL), and the mixture solution was extracted with ethyl acetate (3 × 15.0 mL). The combined organic layers were washed with water, brine, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel to afford product.


Key Words

alkylsilanes, vinylsilanes, manganese


ID: J54-Y2021