AIBN as an Electrophilic Reagent for Cyano Group Transfer

AIBN is a convenient electrophilic cyanation reagent for transforming ArLi into ArCN under mild conditions. The addition/fragmentation cascade is controlled by Li···N chelation in which AIBN nitrogens assist in the nearly barrierless fragmentation into the desired ArCN product. Acidic C–H bonds in t...

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Bibliographic Details
Published inJournal of organic chemistry Vol. 88; no. 4; pp. 2648 - 2654
Main Authors Elliott, Quintin, Alabugin, Igor V.
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 17.02.2023
Amer Chemical Soc
Subjects
byproducts
chelation
Chemistry
Chemistry, Organic
density functional theory
hydrazones
Lewis acids
organic chemistry
Physical Sciences
protonation
Science & Technology
CYANATION
CARBON
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Summary:AIBN is a convenient electrophilic cyanation reagent for transforming ArLi into ArCN under mild conditions. The addition/fragmentation cascade is controlled by Li···N chelation in which AIBN nitrogens assist in the nearly barrierless fragmentation into the desired ArCN product. Acidic C–H bonds in the fragmented byproduct partially consume ArLi by protonation. Density functional theory calculations and isotopic labeling probe the mechanism and explain the switch to substituted hydrazones in reactions with BuLi.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:0022-3263
1520-6904
1520-6904
DOI:10.1021/acs.joc.2c02859