Novel synthesis of 3,4-diaminobutanenitriles and 4-amino-2-butenenitriles from 2-(cyanomethyl)aziridines through intermediate aziridinium salts: an experimental and theoretical approach.
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.
D'hooghe
Matthias
M
Department of Organic Chemistry, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium.
Van Speybroeck
Veronique
V
Van Nieuwenhove
Andries
A
Waroquier
Michel
M
De Kimpe
Norbert
N
D000588:Amines / Q000737:chemistry*; D001388:Aziridines / Q000737:chemistry*; D002073:Butanes / Q000737:chemistry*; D003198:Computer Simulation; D003486:Cyanides / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D008745:Methylation; D008958:Models, Molecular; D015394:Molecular Structure; D009570:Nitriles / Q000138:chemical synthesis / Q000737:chemistry*; D012995:Solubility
D000588:Amines; D001388:Aziridines; D002073:Butanes; D003486:Cyanides; D009570:Nitriles; D006859:Hydrogen