Enhancement of Lewis acidity by ligand-defined metal geometry: A catalytic allylation of aldehydes with allyltrimethylsilane

Synthesis

Volumn , Issue 14, 2002, Pages 1956-1958

  Kanai, Motomu ^a,b   Kuramochi, Akiyoshi ^a   Shibasaki, Masakastu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

^b JAPAN SCIENCE AND TECHNOLOGY AGENCY   (Japan)

Author keywords

Allylation; Aluminum; Lewis acid; Ligand; Metal

Indexed keywords

ALDEHYDES; ALUMINUM; COMPLEXATION;

LIGANDS;

SYNTHESIS (CHEMICAL);

ALDEHYDE; ALDEHYDE DERIVATIVE; ALLYLTRIMETHYLSILANE; ALUMINUM DERIVATIVE; LEWIS ACID; LIGAND; METAL;

ACIDITY; ALLYLATION; ARTICLE; CATALYSIS; CHEMICAL REACTION; COMPLEX FORMATION; CONFORMATIONAL TRANSITION; GEOMETRY; STEREOCHEMISTRY;

EID: 0036398440     PISSN: 00397881     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2002-34366     Document Type: Article

References (23)

1. Lewis Acids in Organic Synthesis; Yamamoto, H., Ed.; Wiley-VCH: Weinheim, 2000.
2. (a) Mikami, K.; Kotera, O.; Motoyama, Y.; Sakaguchi, H.; Maruta, M. Synlett 1996, 171.
3. (b) Ishihara, K.; Kubota, M.; Yamamoto, H. Synlett 1996, 265.
4. (c) Marx, A.; Yamamoto, H. Angew. Chem. Int. Ed. 2000, 39, 178.
5. (d) Ishihara, K.; Hiraiwa, Y.; Yamamoto, H. Synlett 2001, 1851; and references cited therein.
6. For other interesting strategies to enhance the catalyst activity of Lewis acid complexes, see: (a) Lewis acid-Brönsted acid combination: Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 1994, 116, 1561. (b) See also: Corey, E. J.; Shibata, T.; Lee, T. W. J. Am. Chem. Soc. 2002, 124, 3808. (c) Lewis base coordination: Denmark, S. E.; Wynn, T. J. Am. Chem. Soc. 2001, 123, 6199. (d) Bimetallic system: Asao, N.; Kii, S.; Hanawa, H.; Maruoka, K. Tetrahedron Lett. 1998, 39, 3729. (e) Monomer formation using bulky phenoxy ligands: Maruoka, K.; Ooi, T.; Yamamoto, H. J. Am. Chem. Soc. 1989, 111, 6431.
7. For other interesting strategies to enhance the catalyst activity of Lewis acid complexes, see: (a) Lewis acid-Brönsted acid combination: Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 1994, 116, 1561. (b) See also: Corey, E. J.; Shibata, T.; Lee, T. W. J. Am. Chem. Soc. 2002, 124, 3808. (c) Lewis base coordination: Denmark, S. E.; Wynn, T. J. Am. Chem. Soc. 2001, 123, 6199. (d) Bimetallic system: Asao, N.; Kii, S.; Hanawa, H.; Maruoka, K. Tetrahedron Lett. 1998, 39, 3729. (e) Monomer formation using bulky phenoxy ligands: Maruoka, K.; Ooi, T.; Yamamoto, H. J. Am. Chem. Soc. 1989, 111, 6431.
8. For other interesting strategies to enhance the catalyst activity of Lewis acid complexes, see: (a) Lewis acid-Brönsted acid combination: Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 1994, 116, 1561. (b) See also: Corey, E. J.; Shibata, T.; Lee, T. W. J. Am. Chem. Soc. 2002, 124, 3808. (c) Lewis base coordination: Denmark, S. E.; Wynn, T. J. Am. Chem. Soc. 2001, 123, 6199. (d) Bimetallic system: Asao, N.; Kii, S.; Hanawa, H.; Maruoka, K. Tetrahedron Lett. 1998, 39, 3729. (e) Monomer formation using bulky phenoxy ligands: Maruoka, K.; Ooi, T.; Yamamoto, H. J. Am. Chem. Soc. 1989, 111, 6431.
9. For other interesting strategies to enhance the catalyst activity of Lewis acid complexes, see: (a) Lewis acid-Brönsted acid combination: Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 1994, 116, 1561. (b) See also: Corey, E. J.; Shibata, T.; Lee, T. W. J. Am. Chem. Soc. 2002, 124, 3808. (c) Lewis base coordination: Denmark, S. E.; Wynn, T. J. Am. Chem. Soc. 2001, 123, 6199. (d) Bimetallic system: Asao, N.; Kii, S.; Hanawa, H.; Maruoka, K. Tetrahedron Lett. 1998, 39, 3729. (e) Monomer formation using bulky phenoxy ligands: Maruoka, K.; Ooi, T.; Yamamoto, H. J. Am. Chem. Soc. 1989, 111, 6431.
10. For other interesting strategies to enhance the catalyst activity of Lewis acid complexes, see: (a) Lewis acid-Brönsted acid combination: Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 1994, 116, 1561. (b) See also: Corey, E. J.; Shibata, T.; Lee, T. W. J. Am. Chem. Soc. 2002, 124, 3808. (c) Lewis base coordination: Denmark, S. E.; Wynn, T. J. Am. Chem. Soc. 2001, 123, 6199. (d) Bimetallic system: Asao, N.; Kii, S.; Hanawa, H.; Maruoka, K. Tetrahedron Lett. 1998, 39, 3729. (e) Monomer formation using bulky phenoxy ligands: Maruoka, K.; Ooi, T.; Yamamoto, H. J. Am. Chem. Soc. 1989, 111, 6431.
11. For examples of Lewis acidity enhancement by ligand-defined metal geometry, see: (a) Nelson, S. G.; Kim, B.-K.; Peelen, T. J. J. Am. Chem. Soc. 2000, 122, 9318. (b) Denmark, S. E.; Griedel, B. D.; Coe, D. M.; Schnute, M. E. J. Am. Chem. Soc. 1994, 116, 7026; and references cited therein.
12. For examples of Lewis acidity enhancement by ligand-defined metal geometry, see: (a) Nelson, S. G.; Kim, B.-K.; Peelen, T. J. J. Am. Chem. Soc. 2000, 122, 9318. (b) Denmark, S. E.; Griedel, B. D.; Coe, D. M.; Schnute, M. E. J. Am. Chem. Soc. 1994, 116, 7026; and references cited therein.
13. Fleischer, E. B.; Gebala, A. E.; Levey, A.; Tasker, P. A. J. Org. Chem. 1971, 36, 3042.
14. 3OH (29.0)
15. (b) Bordwell, F. G. Acc. Chem. Res. 1988, 21, 456.
16. These calculations were performed using the UNIVERSAL forcefield (v. 1.02) performed on Cerius 2 4.0 (Molecular Simulations Inc.): (a) Rappé, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard, W. A. III; Skiff, W. M. J. Am. Chem. Soc. 1992, 114, 10024. (b) Casewit, C. J.; Colwell, K. S.; Rappé, A. K. J. Am. Chem. Soc. 1992, 114, 10035. (c) Casewit, C. J.; Colwell, K. S.; Rappé, A. K. J. Am. Chem. Soc. 1992, 114, 10046; An N-methyl analog, instead of 4, was used in these calculations for simplification.
17. These calculations were performed using the UNIVERSAL forcefield (v. 1.02) performed on Cerius 2 4.0 (Molecular Simulations Inc.): (a) Rappé, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard, W. A. III; Skiff, W. M. J. Am. Chem. Soc. 1992, 114, 10024. (b) Casewit, C. J.; Colwell, K. S.; Rappé, A. K. J. Am. Chem. Soc. 1992, 114, 10035. (c) Casewit, C. J.; Colwell, K. S.; Rappé, A. K. J. Am. Chem. Soc. 1992, 114, 10046; An N-methyl analog, instead of 4, was used in these calculations for simplification.
18. These calculations were performed using the UNIVERSAL forcefield (v. 1.02) performed on Cerius 2 4.0 (Molecular Simulations Inc.): (a) Rappé, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard, W. A. III; Skiff, W. M. J. Am. Chem. Soc. 1992, 114, 10024. (b) Casewit, C. J.; Colwell, K. S.; Rappé, A. K. J. Am. Chem. Soc. 1992, 114, 10035. (c) Casewit, C. J.; Colwell, K. S.; Rappé, A. K. J. Am. Chem. Soc. 1992, 114, 10046; An N-methyl analog, instead of 4, was used in these calculations for simplification.
19. The chemical yield decreased when catalyst loading of less than 5 mol% was used, <50% with 2 mol% and no reaction with 1 mol%.
20. 5), toluene, and acetonitrile gave the product in 10%, 50%, and 0% yield, respectively.
21. Unfortunately, the desired allylation did not proceed from aliphatic aldehydes or α, β-unsaturated aldehydes. Cyclic trioxanes were the major products from primary and secondary alkyl substituted aldehydes. No reaction occurred from pivalaldehyde and α, β-unsaturated aldehydes.
22. Hamashima, Y.; Sawada, D.; Nogami, H.; Kanai, M.; Shibasaki, M. Tetrahedron 2001, 57, 805; and references cited therein.
23. Side-reaction pathways mediated by a reagent-derived Lewis acidic silicon are problematic, especially in the case of catalytic enantioselective reactions: Carreira, E. M. In Comprehensive Asymmetric Catalysis, Vol. 3; Jacobsen, E. N.; Pfaltz, A.; Yamamoto, H., Eds.; Springer: Heidelberg, 1999, Chap. 29; the possibility that the Lewis acidic silicon of 8 is the actual catalyst in the present case is unlikely due to the fact that the control catalyst 4-Al did not promote the reaction.