D'hooghe Matthias, Van Speybroeck Veronique, Van Nieuwenhove Andries, Waroquier Michel, De Kimpe Norbert
Department of Organic Chemistry, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium.
J Org Chem. 2007 Jun 22;72(13):4733-40. doi: 10.1021/jo0704210. Epub 2007 May 26.
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.
1-芳甲基-2-(氰基甲基)氮杂环丙烷通过4-(N,N-双(芳甲基)氨基)-3-溴丁腈高产率、高纯度地转化为4-(N,N-双(芳甲基)氨基)-3-(吡咯烷-1-基)丁腈和4-(N,N-双(芳甲基)氨基)-2-丁烯腈。关键步骤包括中间体2-(氰基甲基)氮杂环丙烷鎓盐在乙腈中被溴化物和吡咯烷前所未有的区域特异性开环，且仅在取代的氮杂环丙烷碳原子处开环。基于从头算计算对结果进行了合理的解释。
