Enantioselective Synthesis of Cyclic Secondary Amines through Mo-Catalyzed Asymmetric Ring-Closing Metathesis (ARCM)

Organic Letters

Volumn 5, Issue 25, 2003, Pages 4899-4902

  Dolman, Sarah J ^a   Schrock, Richard R ^a   Hoveyda, Amir H ^b  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

^b BOSTON COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; MOLYBDENUM;

ARTICLE; CATALYSIS; CATALYST; CHIRALITY; ENANTIOSELECTIVITY; METHODOLOGY; RING CLOSING METATHESIS; SYNTHESIS;

AMINES; CATALYSIS; HETEROCYCLIC COMPOUNDS, 3-RING; HYDROCARBONS, CYCLIC; MOLECULAR STRUCTURE; MOLYBDENUM; ORGANOMETALLIC COMPOUNDS; STEREOISOMERISM;

EID: 0346422354     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol036026n     Document Type: Article

References (39)

1. For reviews of catalytic asymmetric olefin metathesis, see: (a) Hoveyda, A. H.; Schrock, R. R. Chem. Eur. J. 2001, 7, 945-950. (b) Schrock, R. R.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2003, 42, 4592-4633.
2. For reviews of catalytic asymmetric olefin metathesis, see: (a) Hoveyda, A. H.; Schrock, R. R. Chem. Eur. J. 2001, 7, 945-950. (b) Schrock, R. R.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2003, 42, 4592-4633.
3. For selected reviews on catalytic olefin metathesis, see: (a) Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-452. (b) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1833-1836. (c) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (d) Alkene Metathesis in Organic Synthesis; Furstner, A., Ed.; Springer: Berlin, 1998. (e) Armstrong, S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371-388. (f) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450. (g) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012-3043. (h) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18-29. (i) Ref 1b.
4. For selected reviews on catalytic olefin metathesis, see: (a) Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-452. (b) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1833-1836. (c) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (d) Alkene Metathesis in Organic Synthesis; Furstner, A., Ed.; Springer: Berlin, 1998. (e) Armstrong, S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371-388. (f) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450. (g) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012-3043. (h) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18-29. (i) Ref 1b.
5. For selected reviews on catalytic olefin metathesis, see: (a) Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-452. (b) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1833-1836. (c) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (d) Alkene Metathesis in Organic Synthesis; Furstner, A., Ed.; Springer: Berlin, 1998. (e) Armstrong, S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371-388. (f) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450. (g) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012-3043. (h) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18-29. (i) Ref 1b.
6. For selected reviews on catalytic olefin metathesis, see: (a) Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-452. (b) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1833-1836. (c) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (d) Alkene Metathesis in Organic Synthesis; Furstner, A., Ed.; Springer: Berlin, 1998. (e) Armstrong, S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371-388. (f) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450. (g) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012-3043. (h) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18-29. (i) Ref 1b.
7. For selected reviews on catalytic olefin metathesis, see: (a) Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-452. (b) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1833-1836. (c) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (d) Alkene Metathesis in Organic Synthesis; Furstner, A., Ed.; Springer: Berlin, 1998. (e) Armstrong, S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371-388. (f) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450. (g) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012-3043. (h) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18-29. (i) Ref 1b.
8. For selected reviews on catalytic olefin metathesis, see: (a) Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-452. (b) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1833-1836. (c) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (d) Alkene Metathesis in Organic Synthesis; Furstner, A., Ed.; Springer: Berlin, 1998. (e) Armstrong, S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371-388. (f) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450. (g) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012-3043. (h) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18-29. (i) Ref 1b.
9. For selected reviews on catalytic olefin metathesis, see: (a) Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-452. (b) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1833-1836. (c) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (d) Alkene Metathesis in Organic Synthesis; Furstner, A., Ed.; Springer: Berlin, 1998. (e) Armstrong, S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371-388. (f) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450. (g) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012-3043. (h) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18-29. (i) Ref 1b.
10. For selected reviews on catalytic olefin metathesis, see: (a) Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-452. (b) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1833-1836. (c) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (d) Alkene Metathesis in Organic Synthesis; Furstner, A., Ed.; Springer: Berlin, 1998. (e) Armstrong, S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371-388. (f) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450. (g) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012-3043. (h) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18-29. (i) Ref 1b.
11. For selected reviews on catalytic olefin metathesis, see: (a) Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-452. (b) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1833-1836. (c) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (d) Alkene Metathesis in Organic Synthesis; Furstner, A., Ed.; Springer: Berlin, 1998. (e) Armstrong, S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371-388. (f) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450. (g) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012-3043. (h) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18-29. (i) Ref 1b.
12. For examples of Mo-catalyzed ARCM, see: (a) Alexander, J. B.; La, D. S.; Cefalo, D. R.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 4041-4042. (b) La, D. S.; Alexander, J. B.; Cefalo, D. R.; Graf, D. D.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 9720-9721. (c) Zhu, S. S.; Cefalo, D. R.; La, D. S.; Jamieson, J. Y.; Davis, W. M.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1999, 121, 8251-8259. (d) Cefalo, D. R.; Kiely, A. F.; Wuchrer, M.; Jamieson, J. Y.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 3139-3140. (e) Keily, A. F.; Jernelius, J. A.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 2868-2869.
13. For examples of Mo-catalyzed ARCM, see: (a) Alexander, J. B.; La, D. S.; Cefalo, D. R.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 4041-4042. (b) La, D. S.; Alexander, J. B.; Cefalo, D. R.; Graf, D. D.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 9720-9721. (c) Zhu, S. S.; Cefalo, D. R.; La, D. S.; Jamieson, J. Y.; Davis, W. M.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1999, 121, 8251-8259. (d) Cefalo, D. R.; Kiely, A. F.; Wuchrer, M.; Jamieson, J. Y.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 3139-3140. (e) Keily, A. F.; Jernelius, J. A.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 2868-2869.
14. For examples of Mo-catalyzed ARCM, see: (a) Alexander, J. B.; La, D. S.; Cefalo, D. R.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 4041-4042. (b) La, D. S.; Alexander, J. B.; Cefalo, D. R.; Graf, D. D.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 9720-9721. (c) Zhu, S. S.; Cefalo, D. R.; La, D. S.; Jamieson, J. Y.; Davis, W. M.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1999, 121, 8251-8259. (d) Cefalo, D. R.; Kiely, A. F.; Wuchrer, M.; Jamieson, J. Y.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 3139-3140. (e) Keily, A. F.; Jernelius, J. A.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 2868-2869.
15. For examples of Mo-catalyzed ARCM, see: (a) Alexander, J. B.; La, D. S.; Cefalo, D. R.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 4041-4042. (b) La, D. S.; Alexander, J. B.; Cefalo, D. R.; Graf, D. D.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 9720-9721. (c) Zhu, S. S.; Cefalo, D. R.; La, D. S.; Jamieson, J. Y.; Davis, W. M.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1999, 121, 8251-8259. (d) Cefalo, D. R.; Kiely, A. F.; Wuchrer, M.; Jamieson, J. Y.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 3139-3140. (e) Keily, A. F.; Jernelius, J. A.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 2868-2869.
16. For examples of Mo-catalyzed ARCM, see: (a) Alexander, J. B.; La, D. S.; Cefalo, D. R.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 4041-4042. (b) La, D. S.; Alexander, J. B.; Cefalo, D. R.; Graf, D. D.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 9720-9721. (c) Zhu, S. S.; Cefalo, D. R.; La, D. S.; Jamieson, J. Y.; Davis, W. M.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1999, 121, 8251-8259. (d) Cefalo, D. R.; Kiely, A. F.; Wuchrer, M.; Jamieson, J. Y.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 3139-3140. (e) Keily, A. F.; Jernelius, J. A.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 2868-2869.
17. For examples of Mo-catalyzed AROM, see: (a) La, D. S.; Ford, J. G.; Sattely, E. S.; Bonitatebus, J. P.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 11603-11604. (b) Weatherhead, G. S.; Ford, J. G.; Alexanian, E. J.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, 1828-1829. (c) La, D. S.; Sattely, E. S.; Ford, J. G.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 7767-7778. (d) Tsang, W. C. P.; Jernelius, J. A.; Cortez, A. G.; Weatherhead, G. W.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 2652-2666.
18. For examples of Mo-catalyzed AROM, see: (a) La, D. S.; Ford, J. G.; Sattely, E. S.; Bonitatebus, J. P.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 11603-11604. (b) Weatherhead, G. S.; Ford, J. G.; Alexanian, E. J.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, 1828-1829. (c) La, D. S.; Sattely, E. S.; Ford, J. G.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 7767-7778. (d) Tsang, W. C. P.; Jernelius, J. A.; Cortez, A. G.; Weatherhead, G. W.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 2652-2666.
19. For examples of Mo-catalyzed AROM, see: (a) La, D. S.; Ford, J. G.; Sattely, E. S.; Bonitatebus, J. P.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 11603-11604. (b) Weatherhead, G. S.; Ford, J. G.; Alexanian, E. J.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, 1828-1829. (c) La, D. S.; Sattely, E. S.; Ford, J. G.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 7767-7778. (d) Tsang, W. C. P.; Jernelius, J. A.; Cortez, A. G.; Weatherhead, G. W.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 2652-2666.
20. For examples of Mo-catalyzed AROM, see: (a) La, D. S.; Ford, J. G.; Sattely, E. S.; Bonitatebus, J. P.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 11603-11604. (b) Weatherhead, G. S.; Ford, J. G.; Alexanian, E. J.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, 1828-1829. (c) La, D. S.; Sattely, E. S.; Ford, J. G.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2001, 123, 7767-7778. (d) Tsang, W. C. P.; Jernelius, J. A.; Cortez, A. G.; Weatherhead, G. W.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 2652-2666.
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23. Dolman, S. J.; Sattely, E. S.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 2002, 124, 6991-6997.
24. For reviews regarding the utility of catalytic olefin metathesis in the synthesis of N-containing compounds, see: (a) Phillips, A. J.; Abell, A. D. Aldrichimica Acta 1999, 32, 75-90. (b) Pandit, U. K.; Overkleeft, H. S.; Borer, B. C.; Bieraugel, H. Eur. J. Org. Chem. 1999, 959, 9-968.
25. For reviews regarding the utility of catalytic olefin metathesis in the synthesis of N-containing compounds, see: (a) Phillips, A. J.; Abell, A. D. Aldrichimica Acta 1999, 32, 75-90. (b) Pandit, U. K.; Overkleeft, H. S.; Borer, B. C.; Bieraugel, H. Eur. J. Org. Chem. 1999, 959, 9-968.
26. See Supporting Information for the preparation of starting amines used in this study.
27. Schrock, R. R.; Jamieson, J. Y.; Dolman, S. J.; Miller, S. A.; Davis, W. M.; Hoveyda, A. H. Organometallics 2002, 21, 409-417.
28. For an example of olefin metathesis rate retardation as a result of (proposed) metal-heteroatom chelation, see: Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 7324-7325.
29. (a) Murdzek, J. S.; Schrock, R. R. Organometallics 1987, 6, 1373-1374.
30. (b) Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. J. Am. Chem. Soc. 1990, 112, 3875-3886.
31. For previous examples of enantioselective desymmetrizations of tetraenes through Mo-catalyzed ARCM, see: Weatherhead, G. S.; Houser, J. H.; Ford, J. G.; Jamieson, J. Y.; Schrock, R. R.; Hoveyda, A. H. Tetrahedron Lett. 2000, 41, 9553-9559.
32. (a) VanVeldhuizen, J. J.; Garber, S. B.; Kingsbury, J. S.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 4954-4955.
33. (b) VanVeldhuizen, J. J.; Gillingham, D. G.; Garber, S. B.; Kataoka, O.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 12502-12508.
34. (c) Seiders, T. J.; Ward, D. W.; Grubbs, R. H. Org. Lett. 2001, 3, 3225-3228.
35. (a) Aeilts, S. L.; Cefalo, D. R.; Bonitatebus, P. J.; Houser, J. H.; Hoveyda, A. H.; Schrock, R. R. Angew. Chem., Int. Ed. 2001, 40, 1452-1456.
36. (b) Teng, X.; Cefalo, D. R.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 10779-10784.
37. For example, with second-generation achiral Ru catalysts (Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039-2041; Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, 8168-8179), the RCM illustrated in Table 1 proceed to >90% conversion at 55°C in 1 h (vs 30 min at 22°C with Mo catalysts). For ARCM of 1d (Table 1, entry 4), we find that one chiral Ru catalyst (ref 13b), affords 2d in 14% ee (33% conversion at 55°C after 24 h).
38. For example, with second-generation achiral Ru catalysts (Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039-2041; Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, 8168-8179), the RCM illustrated in Table 1 proceed to >90% conversion at 55°C in 1 h (vs 30 min at 22°C with Mo catalysts). For ARCM of 1d (Table 1, entry 4), we find that one chiral Ru catalyst (ref 13b), affords 2d in 14% ee (33% conversion at 55°C after 24 h).
39. 6, 22°C, 30 min).