Reductive Cross‐Coupling of α‐Oxy Halides Enabled by Thermal Catalysis, Photocatalysis, Electrocatalysis, or Mechanochemistry

Herein, we report a reductive cross‐coupling reaction of α‐oxy halides, simply generated from aldehydes, with a series of C(sp2)‐ and C(sp)‐electrophiles. A wide range of aryl and heteroatom aryl halides, vinyl bromides, alkynyl bromides, and acyl chlorides react with unhindered and hindered aldehyd...

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Bibliographic Details
Published in:Angewandte Chemie 2022-08, Vol.134 (34), p.n/a
Main Authors: Zhu, Chen, Lee, Shao‐Chi, Chen, Haifeng, Yue, Huifeng, Rueping, Magnus
Format: Article
Language:English
Subjects:
Alcohols
Aldehydes
Aromatic compounds
Ball Milling
Bromides
Catalysis
Chemistry
Couplings
Cross coupling
Cross-Coupling Reactions
Density Functional Calculations
Density functional theory
Electrochemistry
Electron transfer
Halides
Ketones
Nozaki–Hiyama–Kishi (NHK) Reaction
Photocatalysis
Reducing agents
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Summary:Herein, we report a reductive cross‐coupling reaction of α‐oxy halides, simply generated from aldehydes, with a series of C(sp2)‐ and C(sp)‐electrophiles. A wide range of aryl and heteroatom aryl halides, vinyl bromides, alkynyl bromides, and acyl chlorides react with unhindered and hindered aldehyde‐derived α‐oxy halides by providing protected alcohols as well as α‐hydroxy ketones. Noteworthy, the reductive couplings are achieved not only through thermal catalysis with the use of metal reductants but also by photocatalysis, electrochemistry, and mechanochemistry. The unrestricted interchange of the four strategies indicates their underlying mechanistic similarities. The generation of NiI intermediate is proposed to be the key point for ketyl radical formation via a single‐electron transfer (SET) event, which was rationalized by an array of control experiments and density functional theory (DFT) calculations. The development of methods to access alcohol derivatives is one of the main concerns of considerable research. Herein, a nickel‐catalyzed reductive cross‐coupling reaction of α‐oxy halides is reported with a series of C(sp2)‐ and C(sp)‐electrophiles, including aryl halides, vinyl bromides, alkynyl bromides, and acyl chlorides with the use of a metal reductant, photocatalysis, electrochemistry, and mechanochemistry.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202204212