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Nucleophile‐Dependent Regio‐ and Stereoselective Ring Opening of 1‐Azoniabicyclo[3.1.0]hexane Tosylate
Author(s) -
Ji MiKyung,
Hertsen Dietmar,
Yoon DooHa,
Eum Heesung,
Goossens Hannelore,
Waroquier Michel,
Van Speybroeck Veronique,
D'hooghe Matthias,
De Kimpe Norbert,
Ha HyunJoon
Publication year - 2014
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201301551
Subject(s) - chemistry , nucleophile , stereoselectivity , aziridine , bicyclic molecule , yield (engineering) , hexane , ring (chemistry) , azide , medicinal chemistry , kinetic control , stereochemistry , regioselectivity , organic chemistry , catalysis , materials science , metallurgy
1‐[(1 R )‐(1‐Phenylethyl)]‐1‐azoniabicyclo[3.1.0]hexane tosylate was generated as a stable bicyclic aziridinium salt from the corresponding 2‐(3‐hydroxypropyl)aziridine upon reaction with p ‐toluenesulfonyl anhydride. This bicyclic aziridinium ion was then treated with various nucleophiles including halides, azide, acetate, and cyanide in CH 3 CN to afford either piperidines or pyrrolidines through regio‐ and stereoselective ring opening, mediated by the characteristics of the applied nucleophile. On the basis of DFT calculations, ring‐opening reactions under thermodynamic control yield piperidines, whereas reactions under kinetic control can yield both piperidines and pyrrolidines depending on the activation energies for both pathways.