Cu-Catalyzed Hydrocarbonylative C–C Coupling of Terminal Alkynes with Alkyl Iodides

A Cu-catalyzed hydrocarbonylative C–C coupling of terminal alkynes with unactivated alkyl iodides has been developed, enabling highly chemo- and regioselective synthesis of unsymmetrical dialkyl ketones. A variety of functional groups are tolerated, and both primary and secondary alkyl iodides react...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 139; no. 30; pp. 10200 - 10203
Main Authors Cheng, Li-Jie, Mankad, Neal P
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 02.08.2017
Amer Chemical Soc
Subjects
alkynes
Chemistry
Chemistry, Multidisciplinary
electron transfer
ketones
moieties
organoiodine compounds
Physical Sciences
regioselectivity
Science & Technology
HALIDES
HYDROBORATION
MECHANISM
CARBONYLATION REACTIONS
INTERMOLECULAR HYDROACYLATION
COPPER
ALDEHYDES
DERIVATIVES
EFFICIENT METHOD
HYDROALKYLATION
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Summary:A Cu-catalyzed hydrocarbonylative C–C coupling of terminal alkynes with unactivated alkyl iodides has been developed, enabling highly chemo- and regioselective synthesis of unsymmetrical dialkyl ketones. A variety of functional groups are tolerated, and both primary and secondary alkyl iodides react well. An autotandem sequence of two Cu-catalyzed processes is proposed: first hydrocarbonylative coupling of the alkyne and the alkyl iodide, followed by reduction of the intermediate unsaturated ketone to the saturated product. Mechanistic experiments indicate that an alkenylcopper intermediate activates the alkyl iodide by single electron transfer to enable a radical carbonylation pathway.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:0002-7863
1520-5126
1520-5126
DOI:10.1021/jacs.7b05205