Nucleophile-dependent regio- and stereoselective ring opening of 1-azoniabicyclo[3.1.0]hexane tosylate
- Author
- Mi-Kyung Ji, Dietmar Hertsen, Doo-Ha Yoon, Heesung Eum, Hannelore Goossens (UGent) , Michel Waroquier (UGent) , Veronique Van Speybroeck (UGent) , Matthias D'hooghe (UGent) , Norbert De Kimpe (UGent) and Hyun-Joon Ha
- Organization
- Abstract
- 1-[(1R)-(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 CH3CN 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.
- Keywords
- TRANSFORMATION, SALTS, REACTIVITY, CYCLIC AMINES, PIPERIDINES, EXPANSION, THEORETICAL RATIONALIZATION, CHIRAL AZIRIDINES, ring opening, ELECTROPHILE-INDUCED CYCLIZATION, SUBSTITUTED 3-FLUOROPIPERIDINES, ring expansion, nucleophilic substitution, heterocycles, density functional theory calculations, aziridines
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Citation
Please use this url to cite or link to this publication: http://hdl.handle.net/1854/LU-5712490
- MLA
- Ji, Mi-Kyung, et al. “Nucleophile-Dependent Regio- and Stereoselective Ring Opening of 1-Azoniabicyclo[3.1.0]Hexane Tosylate.” CHEMISTRY-AN ASIAN JOURNAL, vol. 9, no. 4, 2014, pp. 1060–67, doi:10.1002/asia.201301551.
- APA
- Ji, M.-K., Hertsen, D., Yoon, D.-H., Eum, H., Goossens, H., Waroquier, M., … Ha, H.-J. (2014). Nucleophile-dependent regio- and stereoselective ring opening of 1-azoniabicyclo[3.1.0]hexane tosylate. CHEMISTRY-AN ASIAN JOURNAL, 9(4), 1060–1067. https://doi.org/10.1002/asia.201301551
- Chicago author-date
- Ji, Mi-Kyung, Dietmar Hertsen, Doo-Ha Yoon, Heesung Eum, Hannelore Goossens, Michel Waroquier, Veronique Van Speybroeck, Matthias D’hooghe, Norbert De Kimpe, and Hyun-Joon Ha. 2014. “Nucleophile-Dependent Regio- and Stereoselective Ring Opening of 1-Azoniabicyclo[3.1.0]Hexane Tosylate.” CHEMISTRY-AN ASIAN JOURNAL 9 (4): 1060–67. https://doi.org/10.1002/asia.201301551.
- Chicago author-date (all authors)
- Ji, Mi-Kyung, Dietmar Hertsen, Doo-Ha Yoon, Heesung Eum, Hannelore Goossens, Michel Waroquier, Veronique Van Speybroeck, Matthias D’hooghe, Norbert De Kimpe, and Hyun-Joon Ha. 2014. “Nucleophile-Dependent Regio- and Stereoselective Ring Opening of 1-Azoniabicyclo[3.1.0]Hexane Tosylate.” CHEMISTRY-AN ASIAN JOURNAL 9 (4): 1060–1067. doi:10.1002/asia.201301551.
- Vancouver
- 1.Ji M-K, Hertsen D, Yoon D-H, Eum H, Goossens H, Waroquier M, et al. Nucleophile-dependent regio- and stereoselective ring opening of 1-azoniabicyclo[3.1.0]hexane tosylate. CHEMISTRY-AN ASIAN JOURNAL. 2014;9(4):1060–7.
- IEEE
- [1]M.-K. Ji et al., “Nucleophile-dependent regio- and stereoselective ring opening of 1-azoniabicyclo[3.1.0]hexane tosylate,” CHEMISTRY-AN ASIAN JOURNAL, vol. 9, no. 4, pp. 1060–1067, 2014.
@article{5712490, abstract = {{1-[(1R)-(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 CH3CN 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.}}, author = {{Ji, Mi-Kyung and Hertsen, Dietmar and Yoon, Doo-Ha and Eum, Heesung and Goossens, Hannelore and Waroquier, Michel and Van Speybroeck, Veronique and D'hooghe, Matthias and De Kimpe, Norbert and Ha, Hyun-Joon}}, issn = {{1861-4728}}, journal = {{CHEMISTRY-AN ASIAN JOURNAL}}, keywords = {{TRANSFORMATION,SALTS,REACTIVITY,CYCLIC AMINES,PIPERIDINES,EXPANSION,THEORETICAL RATIONALIZATION,CHIRAL AZIRIDINES,ring opening,ELECTROPHILE-INDUCED CYCLIZATION,SUBSTITUTED 3-FLUOROPIPERIDINES,ring expansion,nucleophilic substitution,heterocycles,density functional theory calculations,aziridines}}, language = {{eng}}, number = {{4}}, pages = {{1060--1067}}, title = {{Nucleophile-dependent regio- and stereoselective ring opening of 1-azoniabicyclo[3.1.0]hexane tosylate}}, url = {{http://doi.org/10.1002/asia.201301551}}, volume = {{9}}, year = {{2014}}, }
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