Catalytic Regiodivergent Kinetic Resolution of Allylic Epoxides: A New Entry to Allylic and Homoallylic Alcohols with High Optical Purity

Journal of Organic Chemistry

Volumn 69, Issue 6, 2004, Pages 2099-2105

  Pineschi, Mauro ^a   Del Moro, Federica ^a   Crotti, Paolo ^a   Di Bussolo, Valeria ^a   Macchia, Franco ^a  

^a UNIVERSITY OF PISA   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOLS; CATALYSIS; CATALYSTS; COPPER; STEREOCHEMISTRY;

KINETIC RESOLUTION; OPTICAL PURITIES;

EPOXY RESINS;

ALCOHOL DERIVATIVE; ALLYL ALCOHOL; ALLYL COMPOUND; COPPER DERIVATIVE; COPPER PHOSPHORAMIDITE; EPOXIDE; PHOSPHORAMIDIC ACID DERIVATIVE; REAGENT; UNCLASSIFIED DRUG; ZINC DERIVATIVE;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHIRALITY; ENANTIOMER; KINETICS; OPTICAL ROTATION; STEREOCHEMISTRY; SYNTHESIS;

EID: 1642332478     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo035674h     Document Type: Article

References (49)

1. For a recent review on kinetic resolution, see: Keith, J. M.; Larrow, J. F.; Jacobsen, E. N. Adv. Synth. Catal. 2001, 1, 5-26 and references therein.
2. For reviews, see: (a) Dehli, J. R.; Gotor, V. Chem. Soc. Rev. 2002, 31, 365.
3. (b) Eames, J. Angew. Chem., Int. Ed. 2000, 39, 885.
4. (a) Vedejs, E.; Chen, X. J. Am. Chem. Soc. 1997, 119, 2584.
5. (b) Cardona, F.; Valenza, S.; Goti, A.; Brandi, A. Eur. J. Org. Chem. 1999, 1319.
6. (c) Pedersen, T. M.; Jensen, J. F.; Humble, R. E.; Rein, T.; Tanner, D.; Bodmann, K.; Reiser, O. Org. Lett. 2000, 2, 535.
7. (a) Alphand, V.; Furstoss, R. J. Org. Chem. 1992, 57, 1306.
8. (b) Adger, B.; Bes, M. T.; Grogan, G.; McCague, R.; Pedragosa-Moreau, S. ; Roberts, S. M.; Villa, R.; Wan, P. W. H.; Willetts, A. J. J. Chem. Soc., Chem. Commun. 1995, 1563.
9. (c) Petit, F.; Furstoss, R. Tetrahedron: Asymmetry 1993, 4, 1341.
10. (d) Gusso, A.; Baccin, C.; Pinna, F.; Strukul, G. Organometallics 1994, 13, 3442.
11. (e) Bolm, C.; Schlingloff, G. J. Chem. Soc., Chem. Commun. 1995, 1247.
12. Cook, G. R.; Sankaranarayanan, S. Org. Lett. 2001, 3, 3531 and pertinent references therein.
13. Doyle, M. P.; Dyatkin, A. B.; Kalinin, A. V.; Ruppar, Q. A.; Martin, S. F.; Spaller, M. R.; Liras, S. J. Am. Chem. Soc. 1995, 117, 11021.
14. While this manuscript was in preparation, an interesting new carbon-carbon bond forming PKR of 4-alkynals catalyzed by Rh(I)/ Tol-BINAP was reported; see: Tanaka, K.; Fu, G. C. J. Am. Chem. Soc. 2003, 125, 8078.
15. Visser, M. S.; Hoveyda, A. H. Tetrahedron 1995, 51, 4383.
16. Bertozzi, F.; Crotti, P.; Macchia, F.; Pineschi, M.; Feringa, B. L. Angew. Chem., Int. Ed. 2001, 40, 930.
17. For the kinetic resolution of allylic epoxides with dialkylzinc reagents and copper-phosphoramidite catalyst, see: (a) Badalassi, F.; Crotti, P.; Macchia, F.; Pineschi, M.; Arnold, A.; Feringa, B. L. Tetrahedron Lett. 1998, 39, 7795.
18. (b) Bertozzi, F.; Crotti, P.; Feringa, B. L.; Macchia, F.; Pineschi, M. Synthesis 2001, 483.
19. For the desymmetrization reaction of symmetrical allylic epoxides, see: (c) Bertozzi, F.; Crotti, P.; Macchia, F.; Pineschi, M.; Arnold, A.; Feringa, B. L. Org. Lett. 2000, 2, 933.
20. (d) Bertozzi, F.; Crotti, P.; Del Moro, F.; Feringa, B. L.; Macchia, F.; Pineschi, M. Chem. Commun. 2001, 2606.
21. Feringa, B. L.; Pineschi, M.; Arnold, L. A.; Imbos, R.; de Vries, A. H. M. Angew. Chem., Int. Ed. 1997, 36, 2620.
22. Chiral ligand 1 was recently used in the iridium-catalyzed allylic etherification and amination of achiral allylic esters: (a) Ohmura, T.; Hartwig, J. F. J. Am. Chem. Soc. 2002, 124, 15164.
23. (b) Lopez, F.; Ohmura, T.; Hartwig, J. F. J. Am. Chem. Soc. 2003, 125, 3426.
24. (S,R,R)-Diastereoisomeric phosphoramidite, derived from (S)-BINOL and (R)-bisphenylethylamine developed by Feringa et al., is to date one of the most effective chiral ligands for the enantioselective addition of dialkylzinc to cyclic enones and for other metal-catalyzed asymmetric processes. For some recent examples, see: (a) Duursma, A.; Minnaard, A. J.; Feringa, B. L. J. Am. Chem. Soc. 2003, 125, 3700 and references therein.
25. (b) Alexakis, A.; Benhaim, C.; Rosset, S.; Humam, M. J. Am. Chem. Soc. 2002, 124, 5262.
26. (c) Jensen, J. F.; Svendsen, B. Y.; la Cour, T. V.; Pedersen, H. L.; Johannsen, M. J. Am. Chem. Soc. 2002, 124, 4558.
27. For a review, see: (d) Feringa, B. L. Acc. Chem. Res. 2000, 33, 346.
28. For a discussion about the installation of an alkyl chain onto cyclopentanoid systems, see: Ito, M.; Matsuumi, M.; Murugesh, M.; Kobayashi, Y. J. Org. Chem. 2001, 66, 5881.
29. Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669.
30. However, this is not always true for all the examined substrates. For example, the use of THF with 1,3-cyclohexadiene monoepoxide 3 afforded a more complex reaction mixture containing also variable amounts of syn adducts.
31. For a recent example concerning the syn addition of organozinc species to cyclic 1,3-diene monoepoxides, see: Xue, S.; Li, Y.; Ha, K.; Yin, W.; Wang, M.; Guo, Q. Org. Lett. 2002, 4, 905.
32. For the determination of absolute and relative configurations of 4-alkylcyclooctanols, see: Del Moro, F.; Crotti, P.; Di Bussolo, V.; Macchia, F.; Pineschi, M. Org. Lett. 2003, 5, 1971.
33. For some recent reports, see: (a) Jacobsen, E. N. Acc. Chem. Res. 2000, 33, 421.
34. (b) Denmark, S. E.; Barsanti, P. A.; Wong, K.-T.; Stavenger, R. A. J. Org. Chem. 1998, 63, 2428.
35. (c) Denmark, S. E.; Wynn, T.; Jellerichs, B. G. Angew. Chem., Int. Ed. 2001, 40, 2225.
36. Attempts to perform the reaction entirely at rt gave 3-cycloheptenone as the major product and only trace amounts of addition compounds.
37. For reviews on the enantioselective formation of quaternary carbon stereocenters, see: (a) Corey, E. J.; Guzmán-Pérez, A. Angew. Chem., Int. Ed. 1998, 37, 388.
38. (b) Christoffers, J.; Mann, A. Angew. Chem., Int. Ed. 2001, 40, 4591.
39. N2′ adducts 37a,b (95% of the crude mixture) was observed. This is a clear, even if indirect, indication that a chiral recognition is present to some extent for isoprene monoepoxide.
40. Tseng, C. C.; Paisley, S. D.; Goering, H. L. J. Org. Chem. 1986, 51, 2884.
41. Lautens, M.; Hiebert, S.; Renaud, J.-L. J. Am. Chem. Soc. 2001, 123, 6834.
42. For a study on the relationship of the double bond configuration between reactants and products in the cross-coupling reactions of allylic substrates with organocopper reagents, see: Underiner, T. L.; Paisley, S. E.; Schmitter, J.; Leshesky, L.; Goering, H. L. J. Org. Chem. 1989, 54, 2369.
43. Olofsson, B.; Somfai, P. J. Org. Chem. 2002, 67, 8574.
44. Annis, G. D.; Ley, S. V.; Self, C. R.; Sivaramakrishnan, R. J. Chem. Soc., Perkin Trans. 1 1981, 270.
45. The E configuration of the double bonds in compounds 51a-c has been established by 1D ROESY spectra (see the Supporting Information).
46. For very recent experimental evidence supporting the incursion of Cu(III) intermediates, see: Karlström, A. S. E.; Bäckwall, J.-E. Chem.-Eur. J. 2001, 7, 1981 and references therein.
47. For the importance of the reductive elimination step in a copper-catalyzed conjugate addition, see: Nakamura, E.; Yamanaka, M.; Mori, S. J. Am. Chem. Soc. 2000, 122, 1826.
48. For a review, see: Marshall, J. A. Chem. Rev. 1989, 89, 1503 and pertinent references therein.
49. Due to the scarcity of direct methods to investigate the reaction pathway, the obtainment of σ-allyl-copper(III) species B, in equilibrium with regioisomeric σ-allyl-copper(III) species C, through a π-allyl complex or a suprafacial 1,3-sigmatropic shift cannot be ruled out. However, the substantial preservation of the stereochemical integrity of the original double bonds present in the SN2 adducts seems to indicate that the reductive elimination step is faster than the eventual incursion of syn/anti isomerization processes.