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

Matthias D'hooghe, Veronique Van Speybroeck, Andries Van Nieuwenhove, Michel Waroquier, Norbert De Kimpe

Journal: The Journal of organic chemistry 2007;72(13):4733-40

PMID: 17530805

Full Text on American Chemical Society View on PubMed

Abstract

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.

Address: Department of Organic Chemistry, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium.

DOI: 10.1021/jo0704210

Link outs

Free resources

Miscellaneous:

https://assays.cancer.gov/CPTAC-317

Subscription / membership required

Full Text Sources:

https://doi.org/10.1021/jo0704210

MeSH Terms: Amines, Aziridines, Butanes, Computer Simulation, Cyanides, Hydrogen, Methylation, Models, Molecular, Molecular Structure, Nitriles, Solubility