Catalytic enantioselective O-H insertion reactions

Journal of the American Chemical Society

Volumn 128, Issue 14, 2006, Pages 4594-4595

  Maier, Thomas C ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE; CATALYSIS; CHEMICAL BOND; ENANTIOSELECTIVITY; REACTION ANALYSIS; STEREOCHEMISTRY;

ALCOHOLS; CATALYSIS; ESTERS; ETHERS; STEREOISOMERISM;

EID: 33646034636     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0607739     Document Type: Article

References (35)

1. For reviews and leading references, see: (a) Davies, H. M. L.; Long, M. S. Angew. Chem., Int. Ed. 2005, 44, 3518-3520.
2. (b) Davies, H. M. L. In Comprehensive Asymmetric Catalysis (Supplement 1); Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: New York, 2004; pp 83-94.
3. (c) Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: New York, 1999; pp 513-603.
4. (d) Davies, H. M. L.; Beckwith, R. E. J. Chem. Rev. 2003, 103, 2861-2903.
5. (e) Müller, P.; Fuirt, C. Chem. Rev. 2003, 103, 2905-2919.
6. Bulugahapitiya, P.; Landais, Y.; Parra-Rapado, L.; Planchenault, D.; Weber, V. J. Org. Chem. 1997, 62, 1630-1641 (8% ee, 59% yield).
7. For examples of diastereoselective O-H insertion reactions, see: (a) Aller, E.; Cox, G. G.; Miller, D. J.; Moody, C. J. Tetrahedron Lett. 1994, 35, 5949-5952.
8. (b) Aller, E.; Brown, D. S.; Cox, G. G.; Miller, D. J.; Moody, C. J. J. Org. Chem. 1995, 60, 4449-4460.
9. (c) Shi, G.-q.; Cao, Z.-y.; Cai, W.-l. Tetrahedron 1995, 51, 5011-5018.
10. (d) Bulugahapitiya, P.; Landais, Y.; Parra-Rapado, L.; Planchenault, D.; Weber, V. J. Org. Chem. 1997, 62, 1630-1641.
11. (e) Miller, D. J.; Moody, C. J.; Morfitt, C. N. Aust. J. Chem. 1999, 52, 97-107.
12. (f) Pansare, S. V.; Jain, R. P.; Bhattacharyya, A. Tetrahedron Lett. 1999, 40, 5255-5258.
13. (g) Moody, C. J.; Morfitt, C. N.; Slawin, A. M. Z. Tetrahedron: Asymmetry 2001, 12, 1657-1661.
14. (h) Jiang, N.; Wang, J.; Chan, A. S. C. Tetrahedron Lett. 2001, 42, 8511-8513.
15. (i) Doyle, M. P.; Yan, M. Tetrahedron Lett. 2002, 43, 5929-5931.
16. (j) Im, C. Y.; Okuyama, T.; Sugimura, T. Chem. Lett. 2005, 1328-1329.
17. (k) Bolm, C.; Saladin, S.; Classen, A.; Kasyan, A.; Veri, E.; Raabe, G. Synlett 2005, 461-464.
18. For reviews of catalyzed insertions of diazo compounds into O-H bonds, see: (a) Doyle, M. P.; McKervey, M. A.; Ye, T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds; Wiley: New York, 1998; Chapters 8.3 and 8.4.
19. (b) Miller, D. J.; Moody, C. J. Tetrahedron 1995, 50, 10811-10843.
20. For leading references to the synthesis and the utility of α-hydroxycarbonyl compounds, see: (a) Janey, J. M. Angew. Chem., Int. Ed. 2005, 44, 4292-4300.
21. (b) Chen, B.-C.; Zhou, P.; Davis, F. A.; Ciganek, E. Org. React. 2003, 62, 1-356.
22. For previous applications of bisazaferrocene ligands in asymmetric catalysis, see: (a) Lo, M. M.-C.; Fu, G. C. J. Am. Chem. Soc. 1998, 120, 10270-10271.
23. (b) Lo, M. M.-C.; Fu, G. C. Tetrahedron 2001, 57, 2621-2634.
24. (c) Lo, M. M.-C.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 4572-4573.
25. For transition metal-catalyzed insertions of diazo compounds into O-H bonds, rhodium, not copper, complexes have generally been the catalysts of choice (see ref 4). For a recent report of an effective copper-based catalyst, see: Morilla, M. E.; Molina, M. J.; Diaz-Requejo, M. M.; Belderrain, T. R.; Nicasio, M. C.; Trofimenko, S.; Perez, P. J. Organometallics 2003, 22, 2914-2918.
26. We do not yet understand the role that water is playing in these reactions.
27. Reactions of α-diazo esters derived from primary alcohols (rather than secondary alcohols, tertiary alcohols, or phenols) proceed with the highest yield and enantioselectivity. Insertions by α-diazo ketones and amides furnish low ee.
28. For the reaction of allyl alcohol, we observe no cyclopropanation of the olefin (see also ref 7).
29. Under our standard conditions, when water is employed as a substrate, O-H insertion occurs in moderate yield (∼55%) and low ee (∼15% ee). Triphenylsilanol and triethylsilanol are unreactive.
30. Notes: (a) Highly electron-rich α-aryl-α-diazo carbonyl compounds are relatively unstable, and they are not suitable substrates under our standard conditions. Insertions of α-pyridyl-α-diazo esters proceed in low ee.
31. (b) Reaction of an alkenyl-substituted (α-styryl) diazoacetate leads to the formation of the desired product in 27% yield and 13% ee. We have not yet attempted to optimize this process.
32. (c) Under our standard conditions, α-alkyl-α-diazoacetates undergo a 1,2-H shift to furnish α,β-unsaturated esters.
33. 2/0.95% 1 leads to a drop in ee (76% ee, 96% yield).
34. For a review of nonlinear effects in asymmetric catalysis, see: Kagan, H. B.; Luukas, T. O. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: New York, 1999; Chapter 4.1.
35. 2OD: 94% yield, 78% ee).