Cyanide Anion as a Leaving Group in Nucleophilic Aromatic Substitution: Synthesis of Quaternary Centers at Azine Heterocycles

Nucleophilic aromatic substitution of 2- or 4-cyanoazines with the anions derived from aliphatic α,α-disubstituted esters and nitriles leads to displacement of the cyanide function. Enabling cyanides to be used as highly active leaving groups in SNAr reactions provides additional flexibility in star...

Full description

Saved in:
Bibliographic Details
Published inJournal of organic chemistry Vol. 78; no. 2; pp. 762 - 769
Main Authors Thompson, Alexander D, Huestis, Malcolm P
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 18.01.2013
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
MECHANISM
COUPLING REACTIONS
NITRILES
ARYL HALIDES
ARYLATION
BONDS
CLEAVAGE
DISCOVERY
CATALYSTS
Online AccessGet full text

Cover

More Information
Summary:Nucleophilic aromatic substitution of 2- or 4-cyanoazines with the anions derived from aliphatic α,α-disubstituted esters and nitriles leads to displacement of the cyanide function. Enabling cyanides to be used as highly active leaving groups in SNAr reactions provides additional flexibility in starting materials for synthesis. We show that, in many cases, the cyanide leaving group is displaced preferentially in the presence of halogens. The resulting heteroaryl iodides, bromides, and chlorides subsequently can be used as handles for further chemical diversification.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:0022-3263
1520-6904
DOI:10.1021/jo302307y