Zr-catalyzed olefin alkylations and allylic substitution reactions with electrophiles

Journal of the American Chemical Society

Volumn 122, Issue 25, 2000, Pages 5977-5983

  De Armas, Judith ^a   Kolis, Stanley P ^a   Hoveyda, Amir H ^a  

^a BOSTON COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE; ALKYL GROUP; ALLYL COMPOUND; BROMINE DERIVATIVE; CHROMENE DERIVATIVE; MAGNESIUM CHLORIDE; TOLUENESULFONIC ACID DERIVATIVE; ZIRCONIUM; ZIRCONOCENE;

ALKYLATION; ARTICLE; CATALYSIS; CHEMICAL BOND; CHEMICAL REACTION; REACTION ANALYSIS; SYNTHESIS;

EID: 0034725379     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja000693j     Document Type: Article

References (32)

1. Zr-catalyzed diastereoselective alkylations: (a) Hoveyda, A. H.; Xu, Z. J. Am. Chem. Soc. 1991, 113, 5079-5080.
2. (b) Morken, J. P.; Hoveyda, A. H. J. Org. Chem. 1993, 58, 4237-4244. Zr-catalyzed enantioselective alkylalions:
3. (c) Morken, J. P.; Didiuk, M. T.; Hoveyda, A. H. J. Am. Chem. Soc. 1993, 115, 6697-6698.
4. (d) Didiuk, M. T.; Johannes, C. W.; Morken, J. P.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 7097-7104. Zr-catalyzed kinetic resolution through enantioselective alkylation:
5. (e) Morken, J. P.; Didiuk, M. T.; Visser, M. S.; Hoveyda, A. H. J. Am. Chem. Soc. 1994, 116, 3123-3124.
6. (f) Visser, M. S.; Harrity, J. P. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1996, 118, 3779-3780.
7. (g) Harrity, J. P. A.; La, D. S.; Cefalo, D. R.; Visser, M. S.; Hoveyda, A. H. J. Am. Chem. Soc. 1998, 120, 2343-2351.
8. Xu, Z.; Johannes, C. W.; Houri, A. F.; La, D. S.; Cogan, D. A.; Hofilena, G. E.; Hoveyda, A. H. J. Am. Chem. Soc. 1997, 119, 10302-10316.
9. Johannes, C. W.; Visser, M. S.; Weatherhead G. S.; Hoveyda, A. H. J. Am. Chem. Soc. 1998, 120, 8340-8347.
10. For previous studies from these laboratories to address this issue, see: (a) Didiuk, M. T.; Morken, J. P.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 7273-7274. (b) Heron, N. M.; Adams, J. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1997, 119, 6205-6206. (c) Adams, J. A.; Heron, N. M.; Koss, A.-M.; Hoveyda, A. H. J. Org. Chem. 1999, 64, 854-860.
11. For previous studies from these laboratories to address this issue, see: (a) Didiuk, M. T.; Morken, J. P.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 7273-7274. (b) Heron, N. M.; Adams, J. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1997, 119, 6205-6206. (c) Adams, J. A.; Heron, N. M.; Koss, A.-M.; Hoveyda, A. H. J. Org. Chem. 1999, 64, 854-860.
12. For previous studies from these laboratories to address this issue, see: (a) Didiuk, M. T.; Morken, J. P.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 7273-7274. (b) Heron, N. M.; Adams, J. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1997, 119, 6205-6206. (c) Adams, J. A.; Heron, N. M.; Koss, A.-M.; Hoveyda, A. H. J. Org. Chem. 1999, 64, 854-860.
13. Houri, A. F.; Didiuk, M. T.; Xu, Z.; Horan, N. R.; Hoveyda, A. H. J. Am. Chem. Soc. 1993, 115, 6614-6624.
14. For example, see: (a) Eisenstein, O.; Hoffmann, R. J. Am. Chem. Soc. 1981, 103, 4308-4320. (b) Fujimoto, H.; Koga, N. Tetrahedron Lett. 1982, 23, 4357-4360.
15. For example, see: (a) Eisenstein, O.; Hoffmann, R. J. Am. Chem. Soc. 1981, 103, 4308-4320. (b) Fujimoto, H.; Koga, N. Tetrahedron Lett. 1982, 23, 4357-4360.
16. Buchwald, S. L.; Nielsen, R. B. J. Am. Chem. Soc. 1988, 110, 3171-3175.
17. (a) Schreiber, S. L.; Crowe, W. E.; Shambayati, S. Tetrahedron Lett. 1990, 31, 5289-5292.
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19. (c) Schore N. E. In Comprehensive Organic Synthesis; Trost, B. M.; Fleming, I., Eds.; Pergamon Press: Oxford: 1991; 1037-1064.
20. Similar to 19, but unlike 22, indene 14 reacts readily with 20 to afford the corresponding alkylation adduct in 88% isolated yield.
21. While our studies were in progress, a related Zr-catalyzed alkylation of terminal styrenes was reported: Terao, J.; Watanabe, T.; Saito, K.; Kambe, N.; Sonoda, N. Tetrahedron Lett. 1998, 39, 9201-9204.
22. Negishi, E.; Nguyen, T.; Maye, J. P.; Choueiri, D.; Suzuki, N.; Takahashi, T. Chem. Lett. 1992, 2367-2370.
23. Recent kinetic studies indicate that allylmagnesium halides can be several orders of magnitude more nueleophilic than alkylmagnesium halides. See: Holm, T. J. Org. Chem. 2000, 65, 1188-1192.
24. 2Zr, ligand exchange with the chromene substrate may be inhibited and the reaction rate reduced. Such unsaturated tosylates and bromides react efficiently with the more reactive 14, but adventitious elimination can presumably more effectively compete with alkylation in the case of less reactive chromenes. The following observations support this contention: (i) The Zr-catalyzed alkylation of 40 proceeds efficiently with 1-bromo-7-octene (80% isolated yield after silica gel chromatography). (ii) The reaction of 40 with 1-tosyloxy-3-butene proceeds further with lower equiv of the electrophile (25% conv with 2 equiv tosylate; 45% conv with 1 equiv tosylate, 100% conv based on tosylate, with 0.7 equiv tosylate). (matrix presented)
25. 1H NMR spectrum of the unpurified product mixture exhibits <2% of any decomposition materials.
26. 2 and n-BuMgCl. This difference in reactivity is likely related to the inability of oxygen atoms in cyclic ethers to coordinate effectively with the transition metal center. See: ref 1d.
27. Formation of a mixture of cis- and trans-olefin isomers in reactions of substituted chromenes (entries 3-5, Table 2) may be due to initial formation of alkylmagnesium halide diastereomers (cf. 60, Scheme 8), which undergo subsequent stereoselective elimination.
28. A similar mechanism involving Zr-alkoxide elimination might also he suggested.
29. For reviews regarding the utility of chiral metallocenes in asymmetric alkylation of olefinic substrates, see: (a) Hoveyda, A. H.; Morken, J. P. Angew. Chem., Int. Ed. Engl. 1996, 35, 1262-1284. (b) Hoveyda, A. H.; Heron, N. M. in Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds; Springer-Verlag: Berlin, 1999; pp 431- 454. For a recent report on an enantioselective Fe-catalyzed olefin alkylation, see: (c) Nakamura, M.; Hirai, A.; Nakamura, E. J. Am. Chem. Soc. 2000, 122, 978-979. For a recent Pd-catalyzed asymmtric addition of dialkylzinc reagents to cyclic allylic ethers, see: (d) Lautens, M.; Renaud, J.-L.; Hiebert, S. J. Am. Chem. Soc. 2000, 122, 1805-1805.
30. For reviews regarding the utility of chiral metallocenes in asymmetric alkylation of olefinic substrates, see: (a) Hoveyda, A. H.; Morken, J. P. Angew. Chem., Int. Ed. Engl. 1996, 35, 1262-1284. (b) Hoveyda, A. H.; Heron, N. M. in Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds; Springer-Verlag: Berlin, 1999; pp 431-454. For a recent report on an enantioselective Fe-catalyzed olefin alkylation, see: (c) Nakamura, M.; Hirai, A.; Nakamura, E. J. Am. Chem. Soc. 2000, 122, 978-979. For a recent Pd-catalyzed asymmtric addition of dialkylzinc reagents to cyclic allylic ethers, see: (d) Lautens, M.; Renaud, J.-L.; Hiebert, S. J. Am. Chem. Soc. 2000, 122, 1805-1805.
31. For reviews regarding the utility of chiral metallocenes in asymmetric alkylation of olefinic substrates, see: (a) Hoveyda, A. H.; Morken, J. P. Angew. Chem., Int. Ed. Engl. 1996, 35, 1262-1284. (b) Hoveyda, A. H.; Heron, N. M. in Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds; Springer-Verlag: Berlin, 1999; pp 431- 454. For a recent report on an enantioselective Fe-catalyzed olefin alkylation, see: (c) Nakamura, M.; Hirai, A.; Nakamura, E. J. Am. Chem. Soc. 2000, 122, 978-979. For a recent Pd-catalyzed asymmtric addition of dialkylzinc reagents to cyclic allylic ethers, see: (d) Lautens, M.; Renaud, J.-L.; Hiebert, S. J. Am. Chem. Soc. 2000, 122, 1805-1805.
32. For reviews regarding the utility of chiral metallocenes in asymmetric alkylation of olefinic substrates, see: (a) Hoveyda, A. H.; Morken, J. P. Angew. Chem., Int. Ed. Engl. 1996, 35, 1262-1284. (b) Hoveyda, A. H.; Heron, N. M. in Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds; Springer-Verlag: Berlin, 1999; pp 431- 454. For a recent report on an enantioselective Fe-catalyzed olefin alkylation, see: (c) Nakamura, M.; Hirai, A.; Nakamura, E. J. Am. Chem. Soc. 2000, 122, 978-979. For a recent Pd-catalyzed asymmtric addition of dialkylzinc reagents to cyclic allylic ethers, see: (d) Lautens, M.; Renaud, J.-L.; Hiebert, S. J. Am. Chem. Soc. 2000, 122, 1805-1805.