Concise Synthesis of 3-(Aminomethyl)pyrrolizidines via an In(OTf)3-Mediated Ring Rearrangement of 2-[2-(1-Pyrrolin-2-yl)-alkyl]aziridines

Jeroen Dolfen; Matthias D’hooghe

doi:10.1055/s-0036-1588404

Synthesis, Table of Contents

Synthesis 2017; 49(10): 2215-2222
DOI: 10.1055/s-0036-1588404

paper

Concise Synthesis of 3-(Aminomethyl)pyrrolizidines via an In(OTf)₃-Mediated Ring Rearrangement of 2-[2-(1-Pyrrolin-2-yl)-alkyl]aziridines

Jeroen Dolfen

SynBioC Research Group, Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, 9000 Ghent, Belgium Email: matthias.dhooghe@UGent.be

,

Matthias D’hooghe*

SynBioC Research Group, Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, 9000 Ghent, Belgium Email: matthias.dhooghe@UGent.be

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Abstract

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Abstract

In this study, an efficient ring rearrangement of 2-[2-(1-pyrrolin-2-yl)alkyl]aziridines, prepared from 2-(bromomethyl)aziridines, toward novel trans- and cis-3-aminomethyl-substituted pyrrolizidines was developed. To that end, addition of In(OTf)₃ as an appropriate Lewis acid catalyst resulted in the formation of intermediate pyrrolizidinium salts via regioselective aziridine ring opening, which were then trapped by a hydride or cyanide nucleophile. Column chromatographic purification allowed the isolation of the major trans-isomers, exclusively.

Key words

pyrrolizidines - aziridines - ring rearrangement - α-aminonitriles - In(OTf)₃

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References

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