Visible light-mediated metal-free alkyl Suzuki-Miyaura coupling of alkyl halides and alkenylboronic acids/esters: a green method for the synthesis of allyl difluoride derivatives

The Suzuki-Miyaura reaction has greatly facilitated the construction of C-C bonds and is well appreciated in medicinal chemistry, yet transition metal residues in this process are an unavoidable challenge. Herein, we report the first visible-light-driven photocatalyst-free coupling reaction of alken...

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Published in:Green chemistry : an international journal and green chemistry resource : GC 2023-05, Vol.25 (9), p.3453-3461
Main Authors: Qu, Chuan-Hua, Yan, Xiao, Li, Shu-Ting, Liu, Jian-Bo, Xu, Zhi-Gang, Chen, Zhong-Zhu, Tang, Dian-Yong, Liu, Huan-Xiang, Song, Gui-Ting
Format: Article
Language:English
Subjects:
Amines
Chemical reactions
Coupling
Covalent bonds
Difluorides
Esters
Green chemistry
Halides
Ketones
Streamlining
Substrates
Transition metals
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Summary:The Suzuki-Miyaura reaction has greatly facilitated the construction of C-C bonds and is well appreciated in medicinal chemistry, yet transition metal residues in this process are an unavoidable challenge. Herein, we report the first visible-light-driven photocatalyst-free coupling reaction of alkenylboronic acids/esters with α-bromodifluoroacylarenes, providing streamlining access to a series of Suzuki coupling products. The reactions proceed under metal-free conditions with a wide substrate scope. Mechanistic experiments and DFT calculation studies revealed that halogen bonding interactions, mainly generated in situ between α-bromodifluoroacylarenes and tertiary amines, could promote the C sp 3 -Br bond homolytic cleavage from difluorobromoaryl ketones. Halogen bonding-assisted C sp 3 -Br homolysis and bromine radical-mediated oxidative deboronation make visible-light-driven photocatalyst-free alkyl Suzuki-Miyaura coupling of alkenylboronic acids/esters with α-bromodifluoroacylarenes accessible.
ISSN:1463-9262
1463-9270
DOI:10.1039/d3gc00368j