Chiral Mo-binol complexes: Activity, synthesis, and structure. Efficient enantioselective six-membered ring synthesis through catalytic metathesis

Journal of the American Chemical Society

Volumn 121, Issue 36, 1999, Pages 8251-8259

  Zhu, S Sherry ^a   Cefalo, Dustin R ^b   La, Daniel S ^b   Jamieson, Jennifer Y ^a   Davis, William M ^a   Hoveyda, Amir H ^b   Schrock, Richard R ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

^b BOSTON COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE; LIGAND; MOLYBDENUM COMPLEX;

ARTICLE; CATALYST; CHEMICAL STRUCTURE; CHIRALITY; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STEREOISOMERISM; SYNTHESIS; TEMPERATURE;

EID: 0033568351     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja991432g     Document Type: Article

References (37)

1. (a) Hoveyda, A. H. Chem. Biol. 1998, 5, R187-R191.
2. (b) Shimizu, K. D.; Snapper, M. L.; Hoveyda, A. H. Chem. Eur. J. 1998, 4, 1885-1889.
3. For selected examples of electronic tuning of transition metalcatalyzed reactions, see: (a) Jacobsen, E. N.; Zhang, W.; Guler, M. L. J. Am. Chem. Soc. 1991, 113, 6703-6704. (b) Rajanbabu, T. V.; Ayers, T. A.; Casalnuovo, A. L. J. Am. Chem. Soc. 1994, 116, 4101-4102. (c) Schnyder, A.; Hintermann, L.; Togni, A. Angew. Chem., Int. Ed. Engl. 1995, 34, 931-933 and references therein.
4. For selected examples of electronic tuning of transition metalcatalyzed reactions, see: (a) Jacobsen, E. N.; Zhang, W.; Guler, M. L. J. Am. Chem. Soc. 1991, 113, 6703-6704. (b) Rajanbabu, T. V.; Ayers, T. A.; Casalnuovo, A. L. J. Am. Chem. Soc. 1994, 116, 4101-4102. (c) Schnyder, A.; Hintermann, L.; Togni, A. Angew. Chem., Int. Ed. Engl. 1995, 34, 931-933 and references therein.
5. For selected examples of electronic tuning of transition metalcatalyzed reactions, see: (a) Jacobsen, E. N.; Zhang, W.; Guler, M. L. J. Am. Chem. Soc. 1991, 113, 6703-6704. (b) Rajanbabu, T. V.; Ayers, T. A.; Casalnuovo, A. L. J. Am. Chem. Soc. 1994, 116, 4101-4102. (c) Schnyder, A.; Hintermann, L.; Togni, A. Angew. Chem., Int. Ed. Engl. 1995, 34, 931-933 and references therein.
6. For a recent example, where structurally related substrates have different optimum chiral catalysts, see: Shimizu, K. D.; Cole, B. M.; Krueger, C. A.; Kuntz, K. W.; Snapper, M. L.; Hoveyda, A. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 1704-1707.
7. (a) Alexander, J. B.; La, D. S.; Cefalo, D. R.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 4041-4042.
8. (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.
9. Related Mo complexes have been used in catalyzing ROMP processes: (a) Totland, K. M.; Boyd, T. J.; Lavoie, G. G.; Davis, W. M.; Schrock, R. R. Macromolecules 1996, 29, 6114-6125. (b) McConville, D. H.; Wolf, J. R.; Schrock, R. R. J. Am. Chem. Soc. 1993, 115, 4413-4414. (c) O'Dell, R.; McConville, D. H.; Hofmeister, G. E.; Schrock, R. R. J. Am. Chem. Soc. 1994, 116, 3414-3423.
10. Related Mo complexes have been used in catalyzing ROMP processes: (a) Totland, K. M.; Boyd, T. J.; Lavoie, G. G.; Davis, W. M.; Schrock, R. R. Macromolecules 1996, 29, 6114-6125. (b) McConville, D. H.; Wolf, J. R.; Schrock, R. R. J. Am. Chem. Soc. 1993, 115, 4413-4414. (c) O'Dell, R.; McConville, D. H.; Hofmeister, G. E.; Schrock, R. R. J. Am. Chem. Soc. 1994, 116, 3414-3423.
11. Related Mo complexes have been used in catalyzing ROMP processes: (a) Totland, K. M.; Boyd, T. J.; Lavoie, G. G.; Davis, W. M.; Schrock, R. R. Macromolecules 1996, 29, 6114-6125. (b) McConville, D. H.; Wolf, J. R.; Schrock, R. R. J. Am. Chem. Soc. 1993, 115, 4413-4414. (c) O'Dell, R.; McConville, D. H.; Hofmeister, G. E.; Schrock, R. R. J. Am. Chem. Soc. 1994, 116, 3414-3423.
12. Attempts at Mo-catalyzed ARCM of 1,7-dienes related to 3 at 22°C (where one alkene is trisubstituted) resulted in exclusive dimer formation (by reaction of terminal alkenes).
13. rel values are calculated by the equation reported by Kagan. See: Kagan, H. B.; Fiaud, J. C. Top. Stereochem. 1988, 18, 249-330. This calculation is only an approximation of the relative rates of reactions of the two enantiomers, as it is based on a first-order equation, where a simultaneous process (dimerization) does not occur (see footnote 8 for dimer definition).
14. By dimeric product we mean the material obtained by catalytic intermolecular cross-coupling of two substrate molecules through their terminal alkenes. The dimeric adduct (mixture of olefin isomers) from diene 5a, shown below, is illustrative. (equation presented)
15. Both antipodes of binaphthol are commercially available (Aldrich Co. and Kankyo Kagaku Center Co., Japan).
16. (a) Lingenfelter, D. S.; Helgeson, R. C.; Cram, D. J. J. Org. Chem. 1981, 46, 393-406.
17. (b) Hu, Q. S.; Vitharana, D.; Ou, L. Tetrahedron: Asymmetry 1995, 6, 2123-2126.
18. 1-Bromo-2,4,6-triisopropylbenzene is commercially available (Alfa/Aesar).
19. Wu, Y.-D.; Peng, Z.-H. J. Am. Chem. Soc. 1997, 119, 8043-8049.
20. Feldman, J.; Schrock, R. R. Prog. Inorg. Chem. 1991, 39, 1-74.
21. The bending caused by steric strain is reinforced by lowering of the overlap between the imido N nonbonding electrons into a Mo d orbital, reducing the triple bond character of the Mo-N bond. Thus, the Mo-N bond regains some of its double bond character to cause the observed change in bond angles. For a review on orbital ineractions involved in the synanti isomerization of this class of Mo complexes, see: Schrock, R. R. In Alkene Metathesis in Organic Synthesis; Furstner, A., Ed.; Springer: Berlin 1998; pp 1-37.
22. (a) Reference 12.
23. (b) Folga, E.; Ziegler, T. Organometallics 1993, 12, 325.
24. (c) Monteyne, K.; Ziegler, T. Organometallics 1998, 17, 5901-5907.
25. (d) Cundari, T. R.; Gordon, M. S. Organometallics 1992, 11, 55-63,
26. (e) Fox, H. H.; Schofield, M. H.; Schrock, R. R. Organometallics 1994, 13, 2804-2815.
27. (a) Schrock, R. R. In Reactions of Coordinated Ligands; Braterman, P. R., Ed.; Plenum: New York, 1986; pp 221-283.
28. (b) Brookhart, M.; Green, M. L. H.; Wong, L. Prog. Inorg. Chem. 1988, 36, 1-124.
29. Schrock, R. R.; Crowe, W. E.; Bazan, G. C.; DiMare, M.; O'Regan, M. B.; Schofield, M. H. Organometallics 1991, 10, 1832-1843.
30. 2; see ref 17.
31. These mechanistic possibilities are based on the theoretically supported assumption that an approaching Lewis base binds to the metal complex through one of the CNO faces (see ref 17).
32. Oskam, J. H.; Schrock, R. R. J. Am. Chem. Soc. 1993, 115, 11831-11845.
33. The identity of the major syn THF-bound diastereomer has not yet been determined.
34. α resonance in free anti-2a is likely to be upfield of that for THF-bound anti-2a on the basis of studies involving other complexes in this general family. See ref 5.
35. For a related study in this area, see: Fujimura, O.; Grubbs, R. H. J. Am. Chem. Soc. 1996, 118, 2499-2500.
36. Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. J. Am. Chem. Soc. 1990, 112, 3875-3886.
37. Gao, Y.; Hanson, R. M.; Klunder, J. M.; Ko, S. Y.; Masamune, H.; Sharpless, K. B. J. Am. Chem. Soc. 1987, 109, 5767-5780 and references therein.