Wynne, Emma L., Clarkson, Guy J. and Shipman, Michael. (2008) Stereocontrolled approach to 1-azabicyclo[4.1.0]heptanes : application to the synthesis of trans-2,6-disubstituted piperidines. Tetrahedron Letters, Volume 49 (Number 2). pp. 250-252. ISSN 0040-4039

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Abstract

Stereocontrolled synthesis of a 1-azabicyclo[4.1.0]heptane is achieved by formation of an NH aziridine from the corresponding 1.2-azido alcohol and subsequent intramolecular conjugate addition onto a tethered alpha,beta-unsaturated ester. Regioselective ring opening of the product at C-7 by heteroatom based nucleophiles yields trans-2,6-disubstituted piperidines in moderate to good yields. (c) 2007 Elsevier Ltd. All rights reserved.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Divisions:	Faculty of Science > Chemistry
Library of Congress Subject Headings (LCSH):	Heterocyclic compounds, Nitrogen, Ring-opening polymerization, Stereochemistry, Aziridines
Journal or Publication Title:	Tetrahedron Letters
Publisher:	Elsevier
ISSN:	0040-4039
Date:	7 January 2008
Volume:	Volume 49
Number:	Number 2
Number of Pages:	3
Page Range:	pp. 250-252
Identification Number:	10.1016/j.tetlet.2007.11.077
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access
Funder:	Engineering and Physical Sciences Research Council (EPSRC), University of Warwick
References:	1. For a monograph, see: Aziridines and Epoxides in Organic Synthesis; Yudin, A. K., Ed.; Wiley-VCH: Weinheim, 2006. 2. For recent reviews, see: Olsen, C. A.; Franzyk, H.; Jaroszewski, J. W. Eur. J. Org. Chem. 2007, 1717–1724; Hu, X. E. Tetrahedron 2004, 60, 2701–2743; Sweeney, J. B. Chem. Soc. Rev. 2002, 31, 247–258; McCoull, W.; Davis, F. A. Synthesis 2000, 1347–1365. 3. Hodgkinson, T. J.; Kelland, L. R.; Shipman, M.; Vile, J. Tetrahedron 1998, 54, 6029–6034. 4. Hediger, M. E. Bioorg. Med. Chem. 2004, 12, 4995–5010. 5. Goujon, J.-Y.; Gueyrard, D.; Compain, P.; Martin, O. R.; Ikeda, K.; Kato, A.; Asano, N. Bioorg. Med. Chem. 2005, 13, 2313–2324. 6. Banwell, M. G.; Lupton, D. W.; Willis, A. C. Aust. J. Chem. 2005, 58, 722–737. 7. Guo, Z. H.; Schultz, A. G. Tetrahedron Lett. 2004, 45, 919–921. 8. Kim, S.; Lee, Y. M.; Lee, J.; Lee, T.; Fu, Y.; Song, Y.; Cho, J.; Kim, D. J. Org. Chem. 2007, 72, 4886–4891. 9. Wu, X.; Toppet, S.; Compernolle, F.; Hoornaert, G. J. Tetrahedron 2003, 59, 1483–1491. 10. Chen, G.; Sasaki, M.; Li, X.; Yudin, A. K. J. Org. Chem. 2006, 71, 6067–6073. 11. For recent examples, see: Alves, M. J.; Fortes, A. G.; Lemos, A.; Martins, C. Synthesis 2005, 555–558; Timen, A. S.; Somfai, P. J. Org. Chem. 2003, 68, 9958–9963; Davis, F. A.; Wu, Y.; Yan, H.; Prasad, K. R.; McCoull, W. Org. Lett. 2002, 4, 655–658. 12. Ittah, Y.; Sasson, Y.; Shahak, I.; Tsaroom, S.; Blum, J. J. Org. Chem. 1978, 43, 4271–4273. 13. The synthesis of the 1-azabicyclo[3.1.0]hexane skeleton of ficellomycin has been achieved using a related approach, see: Paumier, D.; Garcia, M.; Shipman, M.; Muir, J. C. Synlett 2004, 2212–2214. 14. Prepared by oxidation of 5-hexen-1-ol (PCC, CH2Cl2, 18 h, rt), and used directly in the olefination reaction without purification. For full details, see Supplementary data. 15. Hiebl, J.; Kollmann, H.; Rovenszky, F.; Winkler, K. J. Org. Chem. 1999, 64, 1947–1952. 16. The crude NH aziridine was partially characterised (1H NMR and LRMS). However, attempts to purify it by column chromatography on silica resulted in cyclisation to 1. 17. The (2S*,6S*)-stereochemistry of 1 was deduced by NOE measurements (500 MHz, CDCl3). Specifically, strong reciprocal enhancements were seen between H-2 and H-7 [H-2!H-7: 3.8%; H-7!H–2: 4.4%]. Irradiation of H-70 produced enhancements of H-6 (1.7%) and H-7 (9.7%). No NOEs between H-2 and H-6 were observed. These observations confirm a syn-relationship between the aziridine ring and H-2. 18. Crystallographic data (excluding structure factors) for 6 have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 658615. Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK, (fax: +44 0 1223 336033 or e-mail: deposit@ccdc.cam.ac.uk). 19. For cyclisations involving simple x-amino alkenes. See, for example, Banwell, M. G.; Bissett, B. D.; Bui, C. T.; Pham, H. T. T.; Simpson, G. W. Aust. J. Chem. 1998, 51, 9–18; Knapp, S.; Hale, J. J. J. Org. Chem. 1993, 58, 2650– 2651; Knouzi, N.; Vaultier, M.; Toupet, L.; Carrie, R. Tetrahedron Lett. 1987, 28, 1757–1760. 20. For a review, see: Laschat, S.; Dickner, T. Synthesis 2000, 1781–1813.
URI:	http://wrap.warwick.ac.uk/id/eprint/30596

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