Intermolecular Oxidative Radical Addition to Aromatic Aldehydes: Direct Access to 1,4- and 1,5-Diketones via Silver-Catalyzed Ring-Opening Acylation of Cyclopropanols and Cyclobutanols

A novel silver-catalyzed ring-opening acylation of cyclopropanols and cyclobutanols is described. The reaction proceeds under mild and neutral conditions and provides a facile access to nonsymmetric 1,4- and 1,5-diketones in promising yields with broad substrate scope. Mechanistic studies including...

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Published inJournal of organic chemistry Vol. 83; no. 10; pp. 5665 - 5673
Main Authors Che, Chao, Qian, Zhaosheng, Wu, Mingchang, Zhao, Ying, Zhu, Gangguo
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 18.05.2018
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
C BOND-CLEAVAGE
KETONES
ELECTRON-TRANSFER
REGIOSPECIFIC SYNTHESIS
FACILE ACCESS
MECHANISM
CYCLOALKANOLS
1,4-DICARBONYL COMPOUNDS
BETA-DIKETONES
INTRAMOLECULAR ADDITION
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Summary:A novel silver-catalyzed ring-opening acylation of cyclopropanols and cyclobutanols is described. The reaction proceeds under mild and neutral conditions and provides a facile access to nonsymmetric 1,4- and 1,5-diketones in promising yields with broad substrate scope. Mechanistic studies including DFT calculations suggest the involvement of an uncommon water-assisted 1,2-HAT process, which is strongly exothermic and thus promotes addition of carbon radicals to aldehydes. In contrast to traditional reductive radical addition protocols, this work represents the first example of the intermolecular oxidative radical addition to aldehydes, thus offering a novel strategy for the direct synthesis of acyclic ketones from readily accessible aldehydes.
Bibliography:ObjectType-Article-1
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ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.8b00666