Metal–carbene-guided twofold cross-coupling of ethers with chromium catalysis

Fei Fan, Yong Peng, Xiaoyu Zhang, Sha Wang, Zheng Luo, Meiming Luo and Xiaoming Zeng ()
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Fei Fan: Sichuan University
Yong Peng: Sichuan University
Xiaoyu Zhang: Sichuan University
Sha Wang: Sichuan University
Zheng Luo: Sichuan University
Meiming Luo: Sichuan University
Xiaoming Zeng: Sichuan University

Nature Communications, 2024, vol. 15, issue 1, 1-11

Abstract: Abstract Coupling by metal–carbene transfer enables the formation of several different bonds at the carbenoid site, enabling prochiral Csp3 centers that are fundamental three-dimensional substructures for medicines to be forged with increased efficiency. However, strategies using bulk chemicals are rare because of the challenge of breaking two unactivated geminal bonds. Herein, we report the reactivity of ethers to form metal–carbene intermediate by cleavage of α-Csp3–H/Csp3–O bonds, which achieve selective coupling with arylmagnesium bromides and chlorosilanes. These couplings are catalysed by cyclic (alkyl)(amino)carbene-chromium complex and enable the one-step formation of 1,n-arylsilyl alcohols and α-arylated silanes. Mechanistic studies indicate that the in-situ formed low-valent Cr might react with iodobenzene to form phenyl radical species, which abstracts the α-H atom of ether in giving α-oxy radical. The latter combines with Cr by breaking α-Csp3–O bond to afford metal–carbene intermediate, which couples with aryl Grignard and chlorosilane to form two σ-bonds.

Date: 2024
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DOI: 10.1038/s41467-024-50675-5

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