A Novel Enantioselective Access to Enantiomerically Pure Phospholanes Using the Chiral Lithium Amide Base Approach

Journal of Organic Chemistry

Volumn 63, Issue 4, 1998, Pages 912-913

  Hume, Stephen C ^a   Simpkins, Nigel S ^a  

^a UNIVERSITY OF NOTTINGHAM   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000067981     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo972016m     Document Type: Article

References (27)

1. For recent reviews, see: (a) Noyori, R. Asymmetric Catalysis in Organic Synthesis; John Wiley and Sons: New York, 1994. (b) Advanced Asymmetric Synthesis; Stephenson, R., Ed.; Blackie Academic and Professional: London, 1996. (c) Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH Publishers Inc.: New York, 1993. For more complete listings, see the bibliographies in ref 4a-d.
2. For recent reviews, see: (a) Noyori, R. Asymmetric Catalysis in Organic Synthesis; John Wiley and Sons: New York, 1994. (b) Advanced Asymmetric Synthesis; Stephenson, R., Ed.; Blackie Academic and Professional: London, 1996. (c) Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH Publishers Inc.: New York, 1993. For more complete listings, see the bibliographies in ref 4a-d.
3. For recent reviews, see: (a) Noyori, R. Asymmetric Catalysis in Organic Synthesis; John Wiley and Sons: New York, 1994. (b) Advanced Asymmetric Synthesis; Stephenson, R., Ed.; Blackie Academic and Professional: London, 1996. (c) Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH Publishers Inc.: New York, 1993. For more complete listings, see the bibliographies in ref 4a-d.
4. BINAP: Noyori, R.; Takaya, H. Acc. Chem. Res. 1990, 23, 345. DuPHOS: Burk, M. J. J. Am. Chem. Soc. 1991, 113, 8518.
5. BINAP: Noyori, R.; Takaya, H. Acc. Chem. Res. 1990, 23, 345. DuPHOS: Burk, M. J. J. Am. Chem. Soc. 1991, 113, 8518.
6. See, for example: Hayashi, T.; Ohno, A.; Lu, S.; Matsumoto, Y.; Fukuyo, E.; Yanagi, K. J. Am. Chem. Soc. 1994, 116, 4221 and previous papers in the series.
7. 2-symmetric bis-phosphine syntheses, see: (a) Longmire, J. M.; Zhang, X. Tetrahedron Lett. 1997, 38, 1725. (b) Zhu, G.; Cao, P.; Jiang, Q.; Zhang, X. J. Am. Chem. Soc. 1997, 119, 1799. (c) Zhu, G.; Chen, Z.; Jiang, Q.; Xiao, D.; Cao, P.; Zhang, X. J. Am. Chem. Soc. 1997, 119, 3836. See also: (d) Langer, F.; Püntener, K.; Stürmer, R.; Knochel, P. Tetrahedron: Asymmetry 1997, 8, 715.
8. 2-symmetric bis-phosphine syntheses, see: (a) Longmire, J. M.; Zhang, X. Tetrahedron Lett. 1997, 38, 1725. (b) Zhu, G.; Cao, P.; Jiang, Q.; Zhang, X. J. Am. Chem. Soc. 1997, 119, 1799. (c) Zhu, G.; Chen, Z.; Jiang, Q.; Xiao, D.; Cao, P.; Zhang, X. J. Am. Chem. Soc. 1997, 119, 3836. See also: (d) Langer, F.; Püntener, K.; Stürmer, R.; Knochel, P. Tetrahedron: Asymmetry 1997, 8, 715.
9. 2-symmetric bis-phosphine syntheses, see: (a) Longmire, J. M.; Zhang, X. Tetrahedron Lett. 1997, 38, 1725. (b) Zhu, G.; Cao, P.; Jiang, Q.; Zhang, X. J. Am. Chem. Soc. 1997, 119, 1799. (c) Zhu, G.; Chen, Z.; Jiang, Q.; Xiao, D.; Cao, P.; Zhang, X. J. Am. Chem. Soc. 1997, 119, 3836. See also: (d) Langer, F.; Püntener, K.; Stürmer, R.; Knochel, P. Tetrahedron: Asymmetry 1997, 8, 715.
10. 2-symmetric bis-phosphine syntheses, see: (a) Longmire, J. M.; Zhang, X. Tetrahedron Lett. 1997, 38, 1725. (b) Zhu, G.; Cao, P.; Jiang, Q.; Zhang, X. J. Am. Chem. Soc. 1997, 119, 1799. (c) Zhu, G.; Chen, Z.; Jiang, Q.; Xiao, D.; Cao, P.; Zhang, X. J. Am. Chem. Soc. 1997, 119, 3836. See also: (d) Langer, F.; Püntener, K.; Stürmer, R.; Knochel, P. Tetrahedron: Asymmetry 1997, 8, 715.
11. sBuLi-sparteine, has been described; see: Muci, A. R.; Campos, K. R.; Evans, D. A. J. Am. Chem. Soc. 1995, 117, 9075.
12. (b) Chiral lithium amides have been shown to be ineffective with acyclic phosphine oxides; see: O'Brien, P.; Warren, S. Synlett 1996, 579.
13. Complementary studies of enantioselective protonation of metalated phosphine oxides have appeared; see: (a) Vedejs, E.; Garcia-Rivas, J. A. J. Org. Chem. 1994, 59, 6517. (b) Guillen, F.; Moinet, C.; Fiaud, J-C. Bull. Soc. Chim. Fr. 1997, 134, 371 (this report concerns the phospholane system employed in our work). See also ref 5b.
14. Complementary studies of enantioselective protonation of metalated phosphine oxides have appeared; see: (a) Vedejs, E.; Garcia-Rivas, J. A. J. Org. Chem. 1994, 59, 6517. (b) Guillen, F.; Moinet, C.; Fiaud, J-C. Bull. Soc. Chim. Fr. 1997, 134, 371 (this report concerns the phospholane system employed in our work). See also ref 5b.
15. (a) Armer, R.; Begley, M. J.; Cox, P. J.; Persad, A.; Simpkins, N. S. J. Chem. Soc., Perkin Trans. 1 1993, 3099.
16. (b) Blake, A. J.; Westaway, S. M.; Simpkins, N. S. Synlett 1997, 919.
17. Fiaud, J-C.; Legros, J-Y. Tetrahedron Lett. 1991, 32, 5089.
18. 2O, ≥ 99% ee, 40% recovery.
19. (a) Marinetti, A.; Kruger, V.; Le Menn, C.; Ricard, L. J. Organomet. Chem. 1996, 522, 223 and references therein.
20. For related results involving phospholanic acid derivatives, see: (b) Polniaszek, R. P. J. Org. Chem. 1992, 57, 5189. In some cases the stereochemical outcome seems not to have been assigned; see: Mathey, F.; Muller, G.; Bonnard., H. Bull. Soc. Chim. Fr. 1972, 4021.
21. For related results involving phospholanic acid derivatives, see: (b) Polniaszek, R. P. J. Org. Chem. 1992, 57, 5189. In some cases the stereochemical outcome seems not to have been assigned; see: Mathey, F.; Muller, G.; Bonnard., H. Bull. Soc. Chim. Fr. 1972, 4021.
22. The intermediate lithiated phosphine oxide would be expected to be configurationally unstable, on the basis of previous studies; see O'Brien, P.; Warren, S. Tetrahedron Lett. 1995, 36, 8473. Our results can be interpreted as a highly diastereoselective electrophilic quench of the intermediate, leading to substitution with overall retention. Only in the case of anion protonation have we seen substitution with inversion, in accord with the observations of Fiaud and co-workers (see ref 5b).
23. The absolute configurations for 5e and 5f were established by the collection of low-temperature data, including Friedel equivalents, and by refinement of a Flack parameter (values 0.05(8) and 0.0(3), respectively); see: Flack, H. D. Acta Crystallogr., Sect. A 1983, 39, 876. We thank Drs. W-S. Li and A. J. Blake of this department for these determinations; full details will be published elsewhere.
24. Compound 6a was formed as a 15:1 mixture of diastereomers at the new carbinol center.
25. Naumann, L.; Zon, G.; Mislow, K. J. Am. Chem. Soc. 1969, 91, 7012.
26. At present we have not proved that the phosphine oxide reduction has occurred with retention of configuration.
27. 2-symmetry and asymmetric induction, see: Whitesell, J. K. Chem. Rev. 1989, 89, 1581.