Design and synthesis of the first spiro bis(isoxazoline) derivatives as asymmetric ligands

Organic Letters

Volumn 1, Issue 11, 1999, Pages 1795-1797

  Arai, Midori A ^a   Arai, Takayoshi ^a   Sasai, Hiroaki ^a  

^a OSAKA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001760946     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol9902881     Document Type: Article

References (26)

1. (a) Sainsbury, M. Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.: Pergamon Press: Oxford, 1991; Vol. 8, pp 646-648.
2. (b) Curran, D. P. Advances in Cycloaddition; Curran, D. P., Ed.: JAI Press: Greenwich, CT, 1988; Vol. 1, pp 129-189.
3. (c) Padwa, A.; Schoffstall, A. M. Advances in Cycloaddition; Curran, D. P., Ed.: JAI Press: Greenwich, CT, 1988; Vol. 2, pp 28-46.
4. (d) Kozikowski, A. P. Acc. Chem. Res. 1984, 17, 410-416.
5. Acidic ligands bearing isoxazoline moiety: (a) Deshmukh, B. K.; Kharat, R. B. Bull. Chem. Soc. Jpn. 1979, 52, 584-587.
6. (b) Athappan, P. R.; Shanthi, P.; Natarajan, C. Indian J. Chem., Sect. A 1995, 34A, 648-651.
7. (c) Lampeka, R.; Mihan, S.; Beck, W. Z. Naturforsh., B: Chem. Sci. 1996, 51, 581-587.
8. (d) Raghuwanshi, P. B.; Doshi, A. G.; Narwade, M. L. J. Indian. Chem. Soc. 1996, 73, 21-24 and references therein.
9. Example of chelation control of reaction passway by acylisoxazoline: (a) Wade, P. A.; Price, D. T.; Carroll, P. J.; Dailey, W. P. J. Org. Chem. 1990, 55, 3051-3056.
10. (b) Curran, D. P.; Zhang, J. J. Chem. Soc., Perkin Trans. 1 1991, 2613-2625.
11. (c) Kamimura, A.; Yoshihara, K.; Marumo, S.; Yamamoto, A.; Nishiguchi, T.; Kakehi, A.; Hori, K. J. Org. Chem. 1992, 57, 5403-5413.
12. Ab initio calculations were carried out at the HF/6-31G level with Gaussian 94. Frish, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Callacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian 94, Revision D.4; Gaussian, Inc.: Pittsburgh, PA, 1995.
13. Review of the chiral bis(oxazoline) ligands: Ghosh, A. K.; Mathivanan, P.; Cappiello, J. Tetrahedron: Asymmetry 1998, 9, 1-45.
14. SPRIX is an abbreviation of spiro bis(isoxazoline).
15. Recent remarkable chiral spiro ligands for asymmetric reactions: (a) Srivastava, N.; Mital, A.; Kumar, A. J. Chem. Soc., Chem. Commun. 1992, 493-494.
16. (b) Chan, A. S. C.; Hu, W.; Pai, C.-C.; Lau, C-P.; Jiang, Y.; Mi, A.; Yan, M.; Sun, J.; Lou, R.; Deng, J. J. Am. Chem. Soc. 1997, 119, 9570-9571.
17. Bien, S.; Ovadia, D. J. Org. Chem. 1974, 39, 2258-2260.
18. 2 (1:1) at room temperature overnight.
19. w = 0.070.
20. DAICEL CHIRALPAK AD (φ 2 cm x 25 cm). HPLC conditions: 4 (EtOH 3.0 mL/min, 21 min, 29 min); 5 (EtOH 4.5 mL/min, 30 min, 66 min); 6 (EtOH 3.0 mL/min, 33 min, 39 min).
21. After completion of the reaction, chiral 4 was recovered.
22. 13C NMR spectroscopy after derivatization with 1,2-diphenylethylenediamine. Alexakis, A.; Frutos, J. C.; Mangeney, P. Tetrahedron: Asymmetry 1993, 4, 2431-2434.
23. 2 complex (the mixing ratio of SPRIX:Cu = 1.2:1.0) at -50°C to give the Michael adduct (88% yield with 10% ee, 41% yield with 15% ee, and 79% yield with 42% ee, respectively.)
24. The enantiomeric excesses of Michael adduct were not largely affected by the ligand/Cu ratio from 1/1 to 3.3/1.
25. 2 complex.
26. w = 0.050.