Base-Induced Ring Opening of Aza- and Thiaoxa[3.2.1] and -[3.3.1]bicycles as an Enantioselective Approach to Azepines, Thiepines, and Thiocines

Journal of Organic Chemistry

Volumn 62, Issue 21, 1997, Pages 7080-7081

  Lautens, Mark ^a   Fillion, Eric ^a   Sampat, Michael ^a  

^a UNIVERSITY OF TORONTO   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000337796     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo971474s     Document Type: Article

References (42)

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6. (a) For a review on the synthesis of chiral compounds by bond disconnection, see: Gais, H.-J. In Methods of Organic Chemistry (Houben-Weyl), 1996, Vol. E 21a, Part C, p 589. (b) For a recent review on the synthesis and reactions of oxabicyclic systems, see: Chiu, P.; Lautens, M. Topics in Current Chemistry; Springer-Verlag: Berlin, 1997; Vol. 190, p 1. (c) For the enantioselective desymmetrization of 8-oxabicyclo[3.2.1]octan-3-one, see: Bunn, B. J.; Cox, P. J.; Simpkins, N. S. Tetrahedron 1993, 49, 207. For the enantioselective deprotonation/ring opening reaction of tropinone, see: (d) Majewski, M.; Zheng, G.-Z. Can. J. Chem. 1992, 70, 2618. (e) Majewski, M.; Lazny, R. Tetrahedron Lett. 1994, 35, 3653.
7. (a) For a review on the synthesis of chiral compounds by bond disconnection, see: Gais, H.-J. In Methods of Organic Chemistry (Houben-Weyl), 1996, Vol. E 21a, Part C, p 589. (b) For a recent review on the synthesis and reactions of oxabicyclic systems, see: Chiu, P.; Lautens, M. Topics in Current Chemistry; Springer-Verlag: Berlin, 1997; Vol. 190, p 1. (c) For the enantioselective desymmetrization of 8-oxabicyclo[3.2.1]octan-3-one, see: Bunn, B. J.; Cox, P. J.; Simpkins, N. S. Tetrahedron 1993, 49, 207. For the enantioselective deprotonation/ring opening reaction of tropinone, see: (d) Majewski, M.; Zheng, G.-Z. Can. J. Chem. 1992, 70, 2618. (e) Majewski, M.; Lazny, R. Tetrahedron Lett. 1994, 35, 3653.
8. (a) For a review on the synthesis of chiral compounds by bond disconnection, see: Gais, H.-J. In Methods of Organic Chemistry (Houben-Weyl), 1996, Vol. E 21a, Part C, p 589. (b) For a recent review on the synthesis and reactions of oxabicyclic systems, see: Chiu, P.; Lautens, M. Topics in Current Chemistry; Springer-Verlag: Berlin, 1997; Vol. 190, p 1. (c) For the enantioselective desymmetrization of 8-oxabicyclo[3.2.1]octan-3-one, see: Bunn, B. J.; Cox, P. J.; Simpkins, N. S. Tetrahedron 1993, 49, 207. For the enantioselective deprotonation/ring opening reaction of tropinone, see: (d) Majewski, M.; Zheng, G.-Z. Can. J. Chem. 1992, 70, 2618. (e) Majewski, M.; Lazny, R. Tetrahedron Lett. 1994, 35, 3653.
9. (a) For a review on the synthesis of chiral compounds by bond disconnection, see: Gais, H.-J. In Methods of Organic Chemistry (Houben-Weyl), 1996, Vol. E 21a, Part C, p 589. (b) For a recent review on the synthesis and reactions of oxabicyclic systems, see: Chiu, P.; Lautens, M. Topics in Current Chemistry; Springer-Verlag: Berlin, 1997; Vol. 190, p 1. (c) For the enantioselective desymmetrization of 8-oxabicyclo[3.2.1]octan-3-one, see: Bunn, B. J.; Cox, P. J.; Simpkins, N. S. Tetrahedron 1993, 49, 207. For the enantioselective deprotonation/ring opening reaction of tropinone, see: (d) Majewski, M.; Zheng, G.-Z. Can. J. Chem. 1992, 70, 2618. (e) Majewski, M.; Lazny, R. Tetrahedron Lett. 1994, 35, 3653.
10. (a) For a review on the synthesis of chiral compounds by bond disconnection, see: Gais, H.-J. In Methods of Organic Chemistry (Houben-Weyl), 1996, Vol. E 21a, Part C, p 589. (b) For a recent review on the synthesis and reactions of oxabicyclic systems, see: Chiu, P.; Lautens, M. Topics in Current Chemistry; Springer-Verlag: Berlin, 1997; Vol. 190, p 1. (c) For the enantioselective desymmetrization of 8-oxabicyclo[3.2.1]octan-3-one, see: Bunn, B. J.; Cox, P. J.; Simpkins, N. S. Tetrahedron 1993, 49, 207. For the enantioselective deprotonation/ring opening reaction of tropinone, see: (d) Majewski, M.; Zheng, G.-Z. Can. J. Chem. 1992, 70, 2618. (e) Majewski, M.; Lazny, R. Tetrahedron Lett. 1994, 35, 3653.
11. Thiaoxabicycles: (a) Sohár, P.; Kuszmann, J. Acta Chim. Acad. Sci. Hung. 1975, 86, 285. (b) Koyanagi, T.; Hayami, J.-I.; Kaji, A. Chem. Lett. 1976, 971. (c) Baldwin, J. E.; Crossley, M. J.; Lehtonen, E.-M. M. J. Chem. Soc., Chem. Commun. 1979, 918. Azaoxabicycles: (d) Newth, F. H.; Wiggins, L. F. J. Chem. Soc. 1948, 155. (e) Cope, A. C.; Baxter, W. N. J. Am. Chem. Soc. 1955, 77, 393. (f) Cope, A. C.; Anderson, B. C. J. Am. Chem. Soc. 1955, 77, 995. (g) Kilonda, A.; Dequeker, E.; Compernolle, F.; Delbeke, P.; Toppet, S.; Bila, B.; Hoornaert, G. J. Tetrahedron 1995, 51, 849.
12. Thiaoxabicycles: (a) Sohár, P.; Kuszmann, J. Acta Chim. Acad. Sci. Hung. 1975, 86, 285. (b) Koyanagi, T.; Hayami, J.-I.; Kaji, A. Chem. Lett. 1976, 971. (c) Baldwin, J. E.; Crossley, M. J.; Lehtonen, E.-M. M. J. Chem. Soc., Chem. Commun. 1979, 918. Azaoxabicycles: (d) Newth, F. H.; Wiggins, L. F. J. Chem. Soc. 1948, 155. (e) Cope, A. C.; Baxter, W. N. J. Am. Chem. Soc. 1955, 77, 393. (f) Cope, A. C.; Anderson, B. C. J. Am. Chem. Soc. 1955, 77, 995. (g) Kilonda, A.; Dequeker, E.; Compernolle, F.; Delbeke, P.; Toppet, S.; Bila, B.; Hoornaert, G. J. Tetrahedron 1995, 51, 849.
13. Thiaoxabicycles: (a) Sohár, P.; Kuszmann, J. Acta Chim. Acad. Sci. Hung. 1975, 86, 285. (b) Koyanagi, T.; Hayami, J.-I.; Kaji, A. Chem. Lett. 1976, 971. (c) Baldwin, J. E.; Crossley, M. J.; Lehtonen, E.-M. M. J. Chem. Soc., Chem. Commun. 1979, 918. Azaoxabicycles: (d) Newth, F. H.; Wiggins, L. F. J. Chem. Soc. 1948, 155. (e) Cope, A. C.; Baxter, W. N. J. Am. Chem. Soc. 1955, 77, 393. (f) Cope, A. C.; Anderson, B. C. J. Am. Chem. Soc. 1955, 77, 995. (g) Kilonda, A.; Dequeker, E.; Compernolle, F.; Delbeke, P.; Toppet, S.; Bila, B.; Hoornaert, G. J. Tetrahedron 1995, 51, 849.
14. Thiaoxabicycles: (a) Sohár, P.; Kuszmann, J. Acta Chim. Acad. Sci. Hung. 1975, 86, 285. (b) Koyanagi, T.; Hayami, J.-I.; Kaji, A. Chem. Lett. 1976, 971. (c) Baldwin, J. E.; Crossley, M. J.; Lehtonen, E.-M. M. J. Chem. Soc., Chem. Commun. 1979, 918. Azaoxabicycles: (d) Newth, F. H.; Wiggins, L. F. J. Chem. Soc. 1948, 155. (e) Cope, A. C.; Baxter, W. N. J. Am. Chem. Soc. 1955, 77, 393. (f) Cope, A. C.; Anderson, B. C. J. Am. Chem. Soc. 1955, 77, 995. (g) Kilonda, A.; Dequeker, E.; Compernolle, F.; Delbeke, P.; Toppet, S.; Bila, B.; Hoornaert, G. J. Tetrahedron 1995, 51, 849.
15. Thiaoxabicycles: (a) Sohár, P.; Kuszmann, J. Acta Chim. Acad. Sci. Hung. 1975, 86, 285. (b) Koyanagi, T.; Hayami, J.-I.; Kaji, A. Chem. Lett. 1976, 971. (c) Baldwin, J. E.; Crossley, M. J.; Lehtonen, E.-M. M. J. Chem. Soc., Chem. Commun. 1979, 918. Azaoxabicycles: (d) Newth, F. H.; Wiggins, L. F. J. Chem. Soc. 1948, 155. (e) Cope, A. C.; Baxter, W. N. J. Am. Chem. Soc. 1955, 77, 393. (f) Cope, A. C.; Anderson, B. C. J. Am. Chem. Soc. 1955, 77, 995. (g) Kilonda, A.; Dequeker, E.; Compernolle, F.; Delbeke, P.; Toppet, S.; Bila, B.; Hoornaert, G. J. Tetrahedron 1995, 51, 849.
16. Thiaoxabicycles: (a) Sohár, P.; Kuszmann, J. Acta Chim. Acad. Sci. Hung. 1975, 86, 285. (b) Koyanagi, T.; Hayami, J.-I.; Kaji, A. Chem. Lett. 1976, 971. (c) Baldwin, J. E.; Crossley, M. J.; Lehtonen, E.-M. M. J. Chem. Soc., Chem. Commun. 1979, 918. Azaoxabicycles: (d) Newth, F. H.; Wiggins, L. F. J. Chem. Soc. 1948, 155. (e) Cope, A. C.; Baxter, W. N. J. Am. Chem. Soc. 1955, 77, 393. (f) Cope, A. C.; Anderson, B. C. J. Am. Chem. Soc. 1955, 77, 995. (g) Kilonda, A.; Dequeker, E.; Compernolle, F.; Delbeke, P.; Toppet, S.; Bila, B.; Hoornaert, G. J. Tetrahedron 1995, 51, 849.
17. Thiaoxabicycles: (a) Sohár, P.; Kuszmann, J. Acta Chim. Acad. Sci. Hung. 1975, 86, 285. (b) Koyanagi, T.; Hayami, J.-I.; Kaji, A. Chem. Lett. 1976, 971. (c) Baldwin, J. E.; Crossley, M. J.; Lehtonen, E.-M. M. J. Chem. Soc., Chem. Commun. 1979, 918. Azaoxabicycles: (d) Newth, F. H.; Wiggins, L. F. J. Chem. Soc. 1948, 155. (e) Cope, A. C.; Baxter, W. N. J. Am. Chem. Soc. 1955, 77, 393. (f) Cope, A. C.; Anderson, B. C. J. Am. Chem. Soc. 1955, 77, 995. (g) Kilonda, A.; Dequeker, E.; Compernolle, F.; Delbeke, P.; Toppet, S.; Bila, B.; Hoornaert, G. J. Tetrahedron 1995, 51, 849.
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31. 1H NMR spectrum of the product with that of the enantiomer of 7a using (+)-5c as the chiral base and derivatized in an identical fashion. The same sense of induction was assumed for all the other thiaoxabicyclic models.
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41. For examples of deprotonation-elimination, see: (b) Beak, P.; Lee, W. K. J. Org. Chem. 1993, 58, 1109. (c) Garrido, F.; Mann, A.; Wermuth, C.-G. Tetrahedron Lett. 1997, 38, 63.
42. We have also observed high regioselectivity for the deprotonation of unsymmetrical [3.2.1] and [3.3.1] thiaoxabicycles.