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

Coupling by metal–carbene transfer enables the formation of several different bonds at the carbenoid site, enabling prochiral C sp 3 centers that are fundamental three-dimensional substructures for medicines to be forged with increased efficiency. However, strategies using bulk chemicals are rare be...

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Bibliographic Details
Published in:Nature communications 2024-07, Vol.15 (1), p.6455-11, Article 6455
Main Authors: Fan, Fei, Peng, Yong, Zhang, Xiaoyu, Wang, Sha, Luo, Zheng, Luo, Meiming, Zeng, Xiaoming
Format: Article
Language:English
Subjects:
639/638/403/933
639/638/403/934
639/638/77/888
Alcohols
Bromides
Carbenes
Catalysis
Chemical bonds
Chlorosilanes
Chromium
Cleavage
Couplings
Cross coupling
Ethers
Humanities and Social Sciences
Intermediates
Metals
multidisciplinary
Science
Science (multidisciplinary)
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Summary:Coupling by metal–carbene transfer enables the formation of several different bonds at the carbenoid site, enabling prochiral C sp 3 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-C sp 3 –H/C sp 3 –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-C sp 3 –O bond to afford metal–carbene intermediate, which couples with aryl Grignard and chlorosilane to form two σ-bonds. Harnessing carbenoid intermediates during organic transformations is an essential strategy for catalysis but strategies using bulk chemicals are rare due to the challenge of breaking two unactivated geminal bonds. Here, the authors report the reactivity of readily available ethers to form a metal–carbene intermediate via radical-relay bond cleavage.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-024-50675-5