The fluorine-iminium ion gauche effect: proof of principle and application to asymmetric organocatalysis

Angewandte Chemie - International Edition

Volumn 48, Issue 17, 2009, Pages 3065-3068

  Sparr, Christof ^a   Schweizer, W Bernd ^a   Senn, Hans Martin ^b   Gilmour, Ryan ^a  

^a ETH ZURICH   (Switzerland)

^b UNIVERSITY OF GLASGOW   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

GAUCHE EFFECTS; IMINIUM; ORGANOCATALYSIS; ORGANOCATALYSTS; PREORGANIZATION; PROOF OF PRINCIPLES; REVERSIBLE FORMATION; SECONDARY AMINES; STEREO-SELECTIVE; TRANSIENT INTERMEDIATE; UNSATURATED ALDEHYDES;

ALDEHYDES; AMINES; FLUORINE; REACTION KINETICS;

IONS;

ALDEHYDE; EPOXIDE; FLUORINE; IMINE; ION;

CATALYSIS; CHEMISTRY; STEREOISOMERISM; SYNTHESIS;

ALDEHYDES; CATALYSIS; EPOXY COMPOUNDS; FLUORINE; IMINES; IONS; STEREOISOMERISM;

EID: 70349783652     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200900405     Document Type: Article

References (24)

1. F. Babudri, G. M. Farinola, F. Naso, R. Ragni, Chem. Commun. 2007, 1003-1022.
2. D. W. C. MacMillan, Nature 2008, 455, 304-308.
3. For selected examples, see: a) J. J. Irwin, T.-K. Ha, J. D. Dunitz, Helv. Chim. Acta 1990, 73, 1805 -1817;
4. b) D. OΉagan, C. Bilton, J. A. K. Howard, L. Knight, D. J. Tozer, J. Chem. Soc. Perkin Trans. 2 2000, 605-607;
5. c) C. R. S. Briggs, D. O'Hagan, J. A. K. Howard, D. S. Yufit, J. Fluorine Chem. 2003, 119, 9-13;
6. d)C. R. S. Briggs, M. J. Allen, D. O'Hagan, D. J. Tozer, A. M. Z. Slawin, A. E. Goeta, J. A. K. Howard, Org. Biomol. Chem. 2004, 2, 732-740;
7. e) N. E. J. Gooseman, D. O'Hagan, A. M. Z. Slawin, A. M. Teale, D. J. Tozer, R. J. Young, Chem. Commun. 2006, 3190-3192;
8. f) N. E. J. Gooseman, D. O'Hagan, M. J. G. Peach, A. M. Z. Slawin, D. J. Tozer, R. J. Young, Angew. Chem. 2007, 119, 6008-6012; Angew. Chem. Int. Ed. 2007, 46, 5904-5908.
9. G. Evans, T. J. K. Gibbs, R. L. Jenkins, S. J. Coles, M. B. Hurst-house, J. A. Platts, N. C. O. Tomkinson, Angew. Chem. 2008,120, 2862-2865; Angew. Chem. Int. Ed. 2008, 47, 2820-2823.
10. Y. Li, C. Ni, J. Liu, L. Zhang, J. Zheng, L. Zhu, J. Hu, Org Lett. 2006, 8, 1693-1696. For the X-ray data see the Supporting Information.
11. int = 0.072), R(all) = 0.0796. wR(gí) = 0.1689, Flack parameter =0.05 (4). CCDC 716829 contains the supplementary crys-tallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data- request/cif.
12. D. O'Hagan, F. Royer, M. Tavasli, Tetrahedron: Asymmetry 2000,77,2033-2036.
13. - and (R)-2-(fluorodiphenylmethyl)pyrrolidine are commercially available from Sigma-Aldrich.
14. For the crystal structure, see: A. S. Batsanov, J. A. K. Howard, Acta Crystaüogr. Sect. C 2000, 56, e467-e468.
15. For the X-ray data see the Supporting Information.
16. int= 0.090), R(all) = 0.1046. wR(gt) = 0.1664, Flack parameter=-0.07 (12). CCDC716830 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data- request/cif.
17. J. C Burley, R. Gilmour, T. J. Prior, G. M. Day, Acta Crystaüogr. Sect. C 2008, 64, ol0-ol4.
18. D. Seebach, U. Grošelj, D. M. Badine, W. B. Schweizer, A. K. Beck, Helv. Chim. Acta 2008, 91, 1999-2034.
19. J. B. Brazier, G. Evans, T. J. K. Gibbs, S. J. Coles, M. B. Hurst-house, J. A. Platts, N. C. O. Tomkinson, Org. Lett. 2009, 11,133-136.
20. DFT calculations were performed at the M05-2X/6-311+ G-(2df,p) level of theory with Gaussian 03 (Revision E.01). Full details are given in the Supporting Information.
21. For seminal publications, see: a) M. Marigo, J. Franzén, T. B. Poulsen, W. Zhuang, K. A. Jørgensen, J.. Am. Chem. Soc. 2005, 127, 6964-6965;
22. b) S. Lee, D. W. C MacMillan, Tetrahedron 2006, 62,11413-11424;
23. c) X. Wang, B. List, Angew. Chem. 2008, 120, 1135-1138; Angew. Chem. Int. Ed. 2008, 47, 1119-1122.
24. For an example that involves this catalyst in the epoxidation of α,ß-unsaturated enones, see: A. Lattanzi, Org. Lett. 2005, 7, 2579-2582.