Asymmetric catalysis of epoxide ring-opening reactions

Accounts of Chemical Research

Volumn 33, Issue 6, 2000, Pages 421-431

  Jacobsen, Eric N ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHELATING AGENT; CHROMIUM DERIVATIVE; EPOXIDE; ETHYLENEDIAMINE DERIVATIVE; HEAVY METAL; METAL COMPLEX; MONOMER; ORGANOMETALLIC COMPOUND;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; CHEMISTRY; COMPLEX FORMATION; KINETICS; N,N' DISALICYLIDENEETHYLENEDIAMINE; REACTION ANALYSIS; STEREOCHEMISTRY; STRUCTURE ANALYSIS; SYNTHESIS;

CATALYSIS; CHELATING AGENTS; EPOXY COMPOUNDS; ETHYLENEDIAMINES; KINETICS; METALS, HEAVY; MODELS, MOLECULAR; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS;

EID: 0033920416     PISSN: 00014842     EISSN: None     Source Type: Journal    
DOI: 10.1021/ar960061v     Document Type: Article

References (52)

1. For an up-to-date survey, see: Comprehensive Asymmetric Catalysis, Vol I-III; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: New York, 1999.
2. a) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. Enantioselective Epoxidation of Unfunctionalized Olefins Catalyzed by (salen)Manganese Complexes. J. Am. Chem. Soc. 1990, 112, 2801-2803.
3. (b) Jacobsen, E. N.; Deng, L.; Furukawa, Y.; Martínez, L. E. Enantioselective Catalytic Epoxidation of Cinnamate Esters. Tetrahedron 1994, 50, 4323-4334.
4. (c) Jacobsen, E. N. Transition Metal Catalyzed Oxidations: Asymmetric Epoxidation. In Comprehensive Organometallic Chemistry II; Wilkinson, G., Stone, F. G. A., Abel, E. W., Hegedus, L S., Eds.; Pergamon: New York, 1995; Vol. 12, pp 1097-1135.
5. Groves, J. T.; Myers, R. S. Catalytic Asymmetric Epoxidations with Chiral Iron Porphyrins. J. Am. Chem. Soc. 1983, 107, 5791-5796.
6. Fora discussion, see: Jacobsen, E. N.; Wu, M. H. Epoxidation of Alkenes Other than Allylic Alcohols. In Comprehensive Asymmetric Catalysis, Vol I-III; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: New York, 1999; Vol. II, Chapter 18.2.
7. Groves, J. T.; Han, Y.; Van Engen, D. V. Coordination of Styrene Oxide to a Sterically Hindered Ruthenium(II) Porphyrin. J. Chem. Soc., Chem. Commun. 1990, 436-437.
8. Emziane, M.; Sutowardoyo, K. I.; Sinou, D. Asymmetric Ring-Opening of Cyclohexene Oxide with Trimethylsilyl Azide in the Presence of Titanium Isopropoxide/Chiral Ligand J. Organomet. Chem. 1988, 346, C7-C10.
9. Nugent, W. A. Chiral Lewis Acid Catalysis. Enantioselective Addition of Azide to Meso Epoxides. J. Am. Chem. Soc. 1992, 114, 2768-2769.
10. 3 to cyclohexene oxide can by no means be considered a privileged reaction, Nugent's earlier success with a very different catalyst system assured us that highly enantioselective catalysis of this transformation was at least an attainable goal.
11. Martínez, L. E.; Leighton, J. L.; Carsten, D. H.; Jacobsen, E. N. Highly Enantioselective Ring Opening of Epoxides Catalyzed by Chiral (salen)Cr(III) Complexes. J. Am. Chem. Soc. 1995, 117, 5897-5898.
12. In the reported X-ray crystal structures of Mn, Cr, Co, and Al complexes of 1, the ligand adopts a similar conformation in all cases. See: (a) Pospisil, P. J.; Carsten, D. H.; Jacobsen, E. N. X-ray Structural Studies of Highly Enantioselective Mn(salen) Epoxidation Catalysts. Chem. Eur. J. 1996, 2, 974-980.
13. (b) Hansen, K. B.; Leighton, J. L.; Jacobsen, E. N. On the Mechanism of Asymmetric Nucleophilic Ring-Opening of Epoxides Catalyzed by (Salen)Cr(III) Complexes. J. Am. Chem. Soc. 1996, 118, 10924-10925.
14. (c) Sigman, M. S.; Jacobsen, E. N. Unpublished results ([salen]Al(III) complex).
15. (d) Leung, W.-H.; Chan, E. Y. Y.; Chow, E. K. F.; Williams, I. D.; Peng, S.-M. Metal Complexes of a Chiral Quadridentate Schiff Base. J. Chem. Soc., Dalton Trans. 1996, 1229-1236.
16. (a) Leighton, J. L.; Jacobsen, E. N. Efficient Synthesis of (R)-4-Trimethylsilyloxy-2-cyclopenenone by Enantioselective Catalytic Epoxide Ring Opening. J. Org. Chem. 1996, 61, 389-390.
17. (b) Martinez, L. E., Nugent, W. A., Jacobsen, E. N. Highly Efficient and Enantioselective Synthesis of Carbocyclic Nucleoside Analogues Using Selective Early Transition Metal Catalysis. J. Org. Chem. 1996, 61, 7963-7966.
18. (c) Wu, M. H., Jacobsen, E. N. An Efficient Formal Synthesis of Balanol via the Asymmtric Epoxide Ring Opening Reaction. Tetrahedron Lett. 1997, 38, 1693-1696.
19. (d) Schaus, S. E.; Larrow, J. F.; Jacobsen, E. N. Practical Synthesis of Enantiopure Cyclic 1,2-Aminoalcohols via Catalytic Asymmetric Ring Opening of Meso Epoxides. J. Org. Chem. 1997, 62, 4197-4199.
20. Martinez, L. E. Ph.D. Thesis, Harvard University, 1997.
21. Kassab, D. J.; Ganem, B. An Enantioselective Synthesis of (-)-Allosamidin by Asymmetric Desymmetrization of a Highly Functionalized meso-Epoxide. J. Org. Chem. 1999, 64, 1782-1783.
22. Trost, B. M. Atom Economy - A Challenge for Organic Synthesis: Homogeneous Catalysis Leads the Way. Angew. Chem., Int. Ed. Engl. 1995, 34, 259-281.
23. Chlorohydrin 5 is obtained with mediocre (<50%) enantioselectivity, and as yet we have been unable to effect highly enantioselective ARO of epoxides with halide sources using metal salen complexes. For important recent breakthroughs in ARO using chloride as nucleophile, see: (a) Denmark, S. E.; Barsanti, P. A.; Wong, K.-T.; Stavenger, R. A. Enantioselective Ring Opening of Epoxides with Silicon Tetrachloride in the Presence of a Chiral Lewis Base. J. Org. Chem. 1998, 63, 2428-2429.
24. (b) Nugent, W. A. Desymmetrization of Meso Epoxides with Halides: A New Catalytic Reaction Based on Mechanistic Insight. J. Am. Chem. Soc. 1998, 120, 7139-7140.
25. Basolo, F.; Pearson, R. G. Mechanism of Inorganic Reactions; Wiley: New York, 1967; Chapter 3.
26. III complexes proceeds more rapidly than in typical Cr(III) systems. See: (a) Prasad, D. R.; Ramasami, T.; Ramaswamy, D.; Santappa, N. Substitution Lability of Chromium(III) Complexes with Ground-State Distortion. Inorg. Chem. 1980, 19, 3181-3182.
27. +, and Their Conjugate Bases with Thiocyanate, Azide, Imidazole, Pyridine, and Nicotinic Acid as Ligands. Inorg. Chem. 1982, 21, 850-854.
28. Konsler, R. G.; Karl, J.; Jacobsen, E. N. Cooperative Asymmetric Catalysis Using Dimeric Salen Complexes. J. Am. Chem. Soc. 1998, 120, 10780-10781.
29. Konsler, R. G.; Jacobsen, E. N. Unpublished results.
30. For a review, see: Hodgson, D. M., Gibbs, A. R.; Lee, G. P. Enantioselective Desymmetrisation of Achiral Epoxides. Tetrahedron 1996, 52, 14361-14384.
31. Annis, D. A.; Helluin, O.; Jacobsen, E. N. Stereochemistry as a Diversity Element: Solid-Phase Synthesis of Cyclic RGD Peptide Derivatives via Asymmetric Catalysis. Angew. Chem., Int. Ed. Engl. 1998, 37, 1907-1909.
32. For reviews, see ref 4 and the following: (a) Katsuki, T. Epoxidation of Allylic Alcohols. In Comprehensive Asymmetric Catalysis, Vol I-III; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: New York, 1999; Chapter 18.1.
33. (b) Aggarwal, V. K. Epoxide Formation of Enones and Aldehydes. Comprehensive Asymmetric Catalysis, Vol I-III; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: New York, 1999; Chapter 18.3.
34. For reviews, see: (a) Kagan, H. B.; Fiaud, J. C. Kinetic Resolution. In Topics in Stereochemistry, Eliel, E. L., Wilen, S. H., Eds.; Wiley: New York, 1987; Vol. 14, p 249.
35. (b) Eliel, E. L.; Wilen, S. H.; Mander, L. M. Stereochemistry of Organic Compounds; Wiley: New York, 1994; pp 395-415.
36. For a review, see: Noyori, R.; Tokunaga, M.; Kitamura, M. Stereoselective Organic Synthesis via Dynamic Kinetic Resolution. Bull. Chem. Soc. Jpn. 1995, 68, 36-56.
37. 3. Practical Synthesis of Aryl Oxazolidinone Antibacterial Agents. Tetrahedron Lett. 1996, 37, 7939-7942.
38. 3. An Efficient, Catalytic Route to 1,2-Aminoalcohols. J. Am. Chem. Soc. 1996, 118, 7420-7421.
39. For application to 2,2-disubstituted epoxides, see: Lebel, H.; Jacobsen, E. N. Chromium Catalyzed Kinetic Resolution of 2,2-Disubstituted Epoxides. Tetrahedron Lett. 1999, 40, 7303.
40. Although our experiments have proceeded without incident, extreme caution should be exercised in the handling of organic and metal azides, particularly with manipulations that involve heating of neat liquids or solid residues.
41. Jacobsen, E. N.; Kakiuchi, F.; Konsler, R. G.; Larrow, J. F.; Tokunaga, M. Enantioselective Catalytic Ring Opening of Epoxides with Carboxylic Acids. Tetrahedron Lett. 1997, 38, 773-776.
42. The acetate complex 3·OAc is certainly a precatalyst, and the catalytically active species is likely to be a hydroxo complex, 3· OH. This species appears to be rather unstable, and our efforts to isolate it have proven unsuccessful thus far. Hong, J., Jacobsen, E. N. Unpublished results.
43. Tokunaga, M.; Larrow, J. F.; Kakiuchi, F.; Jacobsen, E. N. Asymmetric Catalysis with Water: Efficient Kinetic Resolution of Terminal Epoxides by Mans of Catalytic Hydrolysis. Science 1997, 277, 936-938.
44. MacKillop, A. (ChiRex), personal communication.
45. Schaus, S. E.; et al. Manuscript in preparation.
46. Furrow, M. E.; Schaus, S. E.; Jacobsen, E. N. Practical Access to Highly Enantioenriched C-3 Building Blocks via Hydrolytic Kinetic Resolution. J. Org. Chem. 1998, 63, 6776-6777.
47. For an illustration, see: Schaus, S. E.; Brånalt, J. E.; Jacobsen, E. N. Total Synthesis of Muconin by Efficient Assembly of Chiral Building Blocks. J. Org. Chem. 1998, 63, 4876-4877.
48. Ready, J. M.; Jacobsen, E. N. Asymmetric Catalytic Synthesis of α-Aryloxy Alcohols: Kinetic Resolution of Terminal Epoxides via Highly Enantioselective Ring Opening with Phenols. J. Am. Chem. Soc. 1999, 127, 6086-6087.
49. (a) Peukert, S.; Jacobsen, E. N. Enantioselective Parallel Synthesis Using Polymer-Supported Chiral Co(Salen) Complexes. Org. Lett. 1999, 1, 1245-1247.
50. (b) Annis, D. A.; Jacobsen, E. N. Polymer-Supported Chiral Co(Salen) Complexes: Synthetic Applications and Mechanistic Investigations in the Hydrolytic Kinetic Resolution of Terminal Epoxides. J. Am. Chem. Soc. 1999, 121, 4147-4154.
51. (a) Iida, T.; Yamamoto, N.; Matsunaga, S.; Woo, H.-G.; Shibasaki, M. Enantioselective Ring Opening of Epoxides with 4-Methoxy-phenol Catalyzed by Gallium Heterobimetallic Complexes: An Efficient Method for the Synthesis of Optically Active 1,2-Diol Monoethers. Angew. Chem., Int. Ed. Engl. 1998, 37, 2223-2226.
52. (b) McCleland, B. W.; Nugent, W. A.; Finn, M. G. Mechanistic Studies of the Zirconium-Tri2-propanolamine-Catalyzed Enantioselective Addition of Azide to Cyclohexene Oxide. J. Org. Chem. 1998, 63, 6656-6666.