Unactivated C(sp3)–H Bond Functionalization of Alkyl Nitriles with Vinylarenes and Mechanistic Studies

The first example of a metal-free unactivated C­(sp3)–H bond functionalization of alkyl nitriles with terminal vinylarenes to provide γ-ketonitrile derivatives is described. This protocol features simple operations, a broad substrate scope, and atom and step economy. In addition, Cu-catalyzed C­(sp3...

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Published inOrganic letters Vol. 18; no. 23; pp. 5986 - 5989
Main Authors Lan, Xing-Wang, Wang, Nai-Xing, Bai, Cui-Bing, Lan, Cui-Lan, Zhang, Tong, Chen, Shi-Lu, Xing, Yalan
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 02.12.2016
Amer Chemical Soc
Subjects
chemical reactions
chemical structure
Chemistry
Chemistry, Organic
methodology
nitriles
Physical Sciences
Science & Technology
KETONES
ACTIVATED ALKENES
CINNAMIC-ACIDS
METAL-FREE CONDITIONS
ALLYLIC ALCOHOLS
ALPHA
COPPER
RADICAL-ADDITION
C-H BONDS
ALKENYLATION
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Summary:The first example of a metal-free unactivated C­(sp3)–H bond functionalization of alkyl nitriles with terminal vinylarenes to provide γ-ketonitrile derivatives is described. This protocol features simple operations, a broad substrate scope, and atom and step economy. In addition, Cu-catalyzed C­(sp3)–H bond functionalization of azodi­isobutyro­nitrile (AIBN) and analogues with terminal vinylarenes to generate γ-ketonitriles was also studied. A preliminary free-radical pathway was confirmed by capturing an alkyl radical, and a conjugate system was found that can stabilize radical intermediates and be in favor of this transformation. Density functional theory (DFT) calculations also provide important evidence of the free-radical pathway.
Bibliography:ObjectType-Article-1
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content type line 23
ISSN:1523-7060
1523-7052
1523-7052
DOI:10.1021/acs.orglett.6b02692