(-)-Sparteine-Mediated Metalation of Ferrocenesulfonates. The First Case of Double Asymmetric Induction of Ferrocene Planar Chirality

Organic Letters

Volumn 4, Issue 11, 2002, Pages 1935-1938

  Metallinos, Costa ^a   Snieckus, Victor ^a  

^a QUEEN S UNIVERSITY   (Canada)

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ARTICLE;

EID: 0010623733     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol025963c     Document Type: Article

References (38)

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10. (a) For pioneering work, see: Marquarding, D.; Klusacek, H.; Gokel, G.; Hoffman, P.; Ugi, I. J. Am. Chem. Soc. 1970, 92, 5389. For reviews, see:
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14. Price, D.; Simpkins, N. Tetrahedron Lett. 1995, 36, 6135.
15. (a) Tsukazaki, M.; Tinkl, M.; Roglans, A.; Chapell, B. J.; Taylor, N. J.; Snieckus, V. J. Am. Chem. Soc. 1996, 118, 685.
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18. Rebiere, F.; Riant, O.; Ricard, L.; Kagan, H. B. Angew. Chem., Int. Ed. Engl. 1993, 32, 568; Angew. Chem. 1993, 105, 644.
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20. (a) Review: Kagan, H. B.; Diter, P.; Gref, A.; Guillaneux, D.; Masson-Szymczak, A.; Rebiere, F.; Riant, O.; Samuel, O.; Taudien, S. Pure Appl. Chem. 1996, 68, 29.
21. (b) Achiral tert-butylferrocenyl sulfone, upon metalation with n-BuLi/chiral cyclohexanediamine complex, afforded only a racemic product; see: Nishibayashi, Y.; Arikawa, Y.; Ohe, K.; Uemura, S. J. Org. Chem. 1996, 61, 1172.
22. Bonfiglio, J. N. J. Org. Chem. 1986, 51, 2833.
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24. To date, we have avoided sulfonamide DMGs because ferrocenes are known to be sensitive to strongly acidic media that are normally used to hydrolyze sulfonamides: see: (a) Slocum, D. W.; Achermann, W. Synth. React. Inorg. Met.-Org. Chem. 1982, 12, 397 and references therein. However, the advent of the N-cumyl sulfonamide DMG makes this a more attractive pursuit; see: (b) Metallinos, C.; Nerdinger, S.; Snieckus, V. Org. Lett. 1999, 1, 1183.
25. To date, we have avoided sulfonamide DMGs because ferrocenes are known to be sensitive to strongly acidic media that are normally used to hydrolyze sulfonamides: see: (a) Slocum, D. W.; Achermann, W. Synth. React. Inorg. Met.-Org. Chem. 1982, 12, 397 and references therein. However, the advent of the N-cumyl sulfonamide DMG makes this a more attractive pursuit; see: (b) Metallinos, C.; Nerdinger, S.; Snieckus, V. Org. Lett. 1999, 1, 1183.
26. iso-BuLi was made from iso-BuBr according to the method in: Brandsma, L.; Verkruijsse, H. Preparative Polar Organometallic Chemistry 1; Springer-Verlag: New York, 1987; p 17.
27. Discrimination of diastereotopic sulfonyl oxygens has been postulated to rationalize the observed stereoselectivity in chiral Lewis acid-mediated radical reactions; see: Watanabe, Y.; Mase, N.; Furue, R.; Toru, T. Tetrahedron Lett. 2001, 42, 2981.
28. Amplification of the inherent selectivity of a chiral DMG may be tested by metalating both enantiomers in the presence of (-)-sparteine in the expectation of a matched auxiliary/chiral ligand pair effect, the classic phenomenon of double asymmetric induction. For a review, see: Masamune, S.; Choy, W.; Petersen, J. S.; Sita, L. R. Angew. Chem., Int. Ed. Engl. 1985, 24, 1; Angew. Chem. 1985, 97, 32.
29. Amplification of the inherent selectivity of a chiral DMG may be tested by metalating both enantiomers in the presence of (-)-sparteine in the expectation of a matched auxiliary/chiral ligand pair effect, the classic phenomenon of double asymmetric induction. For a review, see: Masamune, S.; Choy, W.; Petersen, J. S.; Sita, L. R. Angew. Chem., Int. Ed. Engl. 1985, 24, 1; Angew. Chem. 1985, 97, 32.
30. For recent examples of matched/mismatched-pair effects in asymmetric synthesis, see: (a) Vetter, A. H.; Berkessel, A. Tetrahedron Lett. 1998, 39, 1741. (b) Koert, U.; Wagner, H.; Pidun, U. Chem. Ber. 1994, 127, 1447.
31. For recent examples of matched/mismatched-pair effects in asymmetric synthesis, see: (a) Vetter, A. H.; Berkessel, A. Tetrahedron Lett. 1998, 39, 1741. (b) Koert, U.; Wagner, H.; Pidun, U. Chem. Ber. 1994, 127, 1447.
32. (a) Rebiere, F.; Samuel, O.; Ricard, L.; Kagan, H. B. J. Org. Chem. 1991, 56, 5991.
33. (b) Annunziata, M.; Capozzi, M.; Cardellicchio, C.; Naso, F.; Spina, G.; Tortorella, P. J. Org. Chem. 2001, 66, 5933.
34. Crystallographic data (excluding structure factors) for this structure have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-162485. Copies of the data can be obtained free of charge upon application to: CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax, (+44) 1223-336-033; e-mail, deposit@ ccdc.cam.ac.uk).
35. (a) Mills, R. J.; Taylor, N. J.; Snieckus, V. J. Org. Chem. 1989, 54, 4372.
36. (b) This experiment received encouragement from the observation that metalaton of 6a using 2.2 equiv of n-BuLi/(-)-sparteine followed by a TMSC1 quench afforded the 2,5-disilylated product in 69% yield: Metallinos, C. Ph.D. Thesis, Queen's University, Kingston, Ontario, 2001.
37. Ahn, K. H.; Cho, C.; Baek, H.; Park, J.; Lee, S. J. Org. Chem. 1996, 61, 4937.
38. 2, CH2Ch, rt, 24 h) giving alkylated product in good yield, but low enantiocontrol (95% yield, 42% ee).