Novel synthesis of 3,4-diaminobutanenitriles and 4-amino-2-butenenitriles from 2-(cyanomethyl)aziridines through intermediate aziridinium salts: An experimental and theoretical approach

被引：32
作者：
D'hooghe, Matthias
Van Speybroeck, Veronique
Van Nieuwenhove, Andries
Waroquier, Michel
De Kimpe, Norbert
机构：
[1] Univ Ghent, Dept Organ Chem, Fac Biosci Engn, B-9000 Ghent, Belgium
[2] Univ Ghent, Theoret Phys Lab, Ctr Mol Modeling, B-9000 Ghent, Belgium
来源：
JOURNAL OF ORGANIC CHEMISTRY | 2007年 / 72卷 / 13期
关键词：
D O I：
10.1021/jo0704210
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
1-Arylmethyl-2-(cyanomethyl)aziridines were transformed into 4-(N,N-bis(arylmethyl)amino)-3-(pyrrolidin-1-yl)butanenitriles and 4-(N,N-bis(arylmethyl)amino)-2-butenenitriles via 4-(N,N-bis(arylmethyl)amino)-3-bromobutanenitriles in high yields and purity. The key steps involve the unprecedented regiospecific ring opening of intermediate 2-(cyanomethyl)aziridinium salts by bromide and pyrrolidine in acetonitrile, exclusively at the substituted aziridine carbon atom. The results were rationalized on the basis of ab initio calculations.
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页码：4733 / 4740
页数：8
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