A general deoxygenation approach for synthesis of ketones from aromatic carboxylic acids and alkenes

The construction of an aryl ketone structural unit by means of catalytic carbon–carbon coupling reactions represents the state-of-the-art in organic chemistry. Herein we achieved the direct deoxygenative ketone synthesis in aqueous solution from readily available aromatic carboxylic acids and alkene...

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Bibliographic Details
Published in:Nature communications 2018-08, Vol.9 (1), p.3517-10, Article 3517
Main Authors: Zhang, Muliang, Xie, Jin, Zhu, Chengjian
Format: Article
Language:English
Subjects:
639/638/403
639/638/403/933
639/638/549
Acids
Activation
Alkenes
Alkenes - chemistry
Aromatic compounds
Carbon
Carboxylic acids
Carboxylic Acids - chemistry
Catalysis
Chemical reactions
Chemical synthesis
Construction
Coupling (molecular)
Cyclophane
Deoxygenation
Humanities and Social Sciences
Ketones
Ketones - chemistry
Macrocyclic Compounds - chemistry
multidisciplinary
Organic chemistry
Oxidation-Reduction
Photoredox catalysis
Redox potential
Science
Science (multidisciplinary)
Zolpidem
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Summary:The construction of an aryl ketone structural unit by means of catalytic carbon–carbon coupling reactions represents the state-of-the-art in organic chemistry. Herein we achieved the direct deoxygenative ketone synthesis in aqueous solution from readily available aromatic carboxylic acids and alkenes, affording structurally diverse ketones in moderate to good yields. Visible-light photoredox catalysis enables the direct deoxygenation of acids as acyl sources with triphenylphosphine and represents a distinct perspective on activation. The synthetic robustness is supported by the late-stage modification of several pharmaceutical compounds and complex molecules. This ketone synthetic strategy is further applied to the synthesis of the drug zolpidem in three steps with 50% total yield and a concise construction of cyclophane-braced 18–20 membered macrocycloketones. It represents not only the advancement for the streamlined synthesis of aromatic ketones from feedstock chemicals, but also a photoredox radical activation mode beyond the redox potential of carboxylic acids. Synthesis of aryl ketones can be generally achieved via C–C coupling strategies. Here, the authors show a deoxygenative coupling of carboxylic acids and alkenes enabled by photoredox catalysis and report a wide scope of products, including bioactive and macrocyclic ketones.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-018-06019-1