Parallel kinetic resolution of 4-alkynals catalyzed by Rh(I)/Tol-BINAP: Synthesis of enantioenriched cyclobutanones and cyclopentenones

Journal of the American Chemical Society

Volumn 125, Issue 27, 2003, Pages 8078-8079

  Tanaka, Ken ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE DERIVATIVE; CYCLOBUTANONE DERIVATIVE; CYCLOPENTENONE DERIVATIVE; RHODIUM COMPLEX;

ARTICLE; CATALYSIS; CHEMICAL REACTION KINETICS; CHIRALITY; ENANTIOMER; ENANTIOSELECTIVITY; HYDROGEN BOND; SYNTHESIS; TECHNIQUE;

EID: 0038344231     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja035489l     Document Type: Article

References (22)

1. Present address: Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan.
2. For reviews of kinetic resolution, see: (a) Keith, J. M.; Larrow, J. F.; Jacobsen, E. N. Adv. Synth. Catal. 2001, 1, 5-26. (b) Hoveyda, A. H.; Didiuk, M. T. Curr. Org. Chem. 1998, 2, 489-526. (c) Kagan, H. B.; Fiaud, J. C. Top. Stereochem. 1988, 18, 249-330.
3. For reviews of kinetic resolution, see: (a) Keith, J. M.; Larrow, J. F.; Jacobsen, E. N. Adv. Synth. Catal. 2001, 1, 5-26. (b) Hoveyda, A. H.; Didiuk, M. T. Curr. Org. Chem. 1998, 2, 489-526. (c) Kagan, H. B.; Fiaud, J. C. Top. Stereochem. 1988, 18, 249-330.
4. For reviews of kinetic resolution, see: (a) Keith, J. M.; Larrow, J. F.; Jacobsen, E. N. Adv. Synth. Catal. 2001, 1, 5-26. (b) Hoveyda, A. H.; Didiuk, M. T. Curr. Org. Chem. 1998, 2, 489-526. (c) Kagan, H. B.; Fiaud, J. C. Top. Stereochem. 1988, 18, 249-330.
5. (a) For reviews, see: Dehli, J. R.; Gotor, V. Chem. Soc. Rev. 2002, 31, 365-370. Earnes, J. Angew. Chem., Int. Ed. 2000, 39, 885-888.
6. (a) For reviews, see: Dehli, J. R.; Gotor, V. Chem. Soc. Rev. 2002, 31, 365-370. Earnes, J. Angew. Chem., Int. Ed. 2000, 39, 885-888.
7. (b) Vedejs, E.; Chen, X. J. Am. Chem. Soc. 1997, 119, 2584-2585.
8. See also: Hayashi, T.; Yamamoto, M.; Ito, Y. Chem. Lett. 1987, 177-180.
9. Tanaka, K.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 10296-10297.
10. For an example, see: Roskamp, E. J.; Johnson, C. R. J. Am. Chem. Soc. 1986, 108, 6062-6063.
11. Enantiopure 4-hydroxycyclopent-2-enones are of interest due to their utility as intermediates in the synthesis of natural products such as prostaglandins and pentenomycins. (a) For a discussion of the emergence of cyclopentenone prostaglandins as important biologically active compounds, see: Roberts, S. M.; Santoro, M. G.; Sickle, E. S. J. Chem. Soc., Perkin Trans. 1 2002, 1735-1742. (b) For leading references on pentenomycins, see: Seepersaud, M.; Al-Abed, Y. Tetrahedron Lett. 2000, 41, 4291-4293.
12. Enantiopure 4-hydroxycyclopent-2-enones are of interest due to their utility as intermediates in the synthesis of natural products such as prostaglandins and pentenomycins. (a) For a discussion of the emergence of cyclopentenone prostaglandins as important biologically active compounds, see: Roberts, S. M.; Santoro, M. G.; Sickle, E. S. J. Chem. Soc., Perkin Trans. 1 2002, 1735-1742. (b) For leading references on pentenomycins, see: Seepersaud, M.; Al-Abed, Y. Tetrahedron Lett. 2000, 41, 4291-4293.
13. (a) For examples of previous routes to nonracemic cyclobutanones, see: Nemoto, H.; Fukumoto, K. Synlett 1997, 863-875. Hiroi, K.; Nakamura, H.; Anzai, T. J. Am. Chem. Soc. 1987, 109, 1249-1250. Houge, C.; Frisque-Hesbain, A. M.; Mockel, A.; Ghosez, L.; Declercq, J. P.; Germain, G.; Van Meerssche, M. J. Am. Chem. Soc. 1982, 104, 2920-2921.
14. (a) For examples of previous routes to nonracemic cyclobutanones, see: Nemoto, H.; Fukumoto, K. Synlett 1997, 863-875. Hiroi, K.; Nakamura, H.; Anzai, T. J. Am. Chem. Soc. 1987, 109, 1249-1250. Houge, C.; Frisque-Hesbain, A. M.; Mockel, A.; Ghosez, L.; Declercq, J. P.; Germain, G.; Van Meerssche, M. J. Am. Chem. Soc. 1982, 104, 2920-2921.
15. (a) For examples of previous routes to nonracemic cyclobutanones, see: Nemoto, H.; Fukumoto, K. Synlett 1997, 863-875. Hiroi, K.; Nakamura, H.; Anzai, T. J. Am. Chem. Soc. 1987, 109, 1249-1250. Houge, C.; Frisque-Hesbain, A. M.; Mockel, A.; Ghosez, L.; Declercq, J. P.; Germain, G.; Van Meerssche, M. J. Am. Chem. Soc. 1982, 104, 2920-2921.
16. (b) For reviews of the use of cyclobutanes in organic synthesis, see: Lee-Ruff, E.; Mladenova, G. Chem. Rev. 2003, 103, 1449-1483. Namyslo, J. C.; Kaufmann, D. E. Chem. Rev. 2003, 103, 1485-1537.
17. (b) For reviews of the use of cyclobutanes in organic synthesis, see: Lee-Ruff, E.; Mladenova, G. Chem. Rev. 2003, 103, 1449-1483. Namyslo, J. C.; Kaufmann, D. E. Chem. Rev. 2003, 103, 1485-1537.
18. The stereochemistry of the olefin has been assigned in analogy with: Iwasawa, N.; Matsuo, T.; Iwamoto, M.; Ikeno, T. J. Am. Chem. Soc. 1998, 120, 3903-3914.
19. Essentially no cyclobutanone is generated when CHIRAPHOS, DUPHOS, BPE, and JOSIPHOS are employed as ligands.
20. Notes: (a) Use of BINAP leads to lower enantiomeric excess. (b) When reactions are stopped at partial conversion, significant quantities of both the cyclobutanone and the cyclopentenone are observed, indicating that the enantiomeric 4-alkynals are reacting in parallel, not sequentially. (c) To date, we have only observed effective parallel kinetic resolutions for 4-alkynals that bear a methoxy group in the 3 position.
21. 2 (1.0 mL) were added, and then the mixture was stirred at rt for 21 h. Next, the solution was concentrated, and the residue was purified by preparative TLC (hexanes:EtOAc = 4: 1), which furnished (S)-2-benzylidene-3-methoxycyclobutanone (35.2 mg, 0. 187 mmol, 47%; 84% ee) and (R)-4-methoxy2-phenylcyclopent-2-enone (33.8 mg, 0.180 mmol, 45%; 88% ee).
22. Thus, as an alternative to a parallel kinetic resolution, one can generate a cyclobutanone in very high ee through a two-step process: kinetic resolution of a 4-alkynal (ref 5), followed by cyclization with the appropriate enantiomer of Rh/Tol-BINAP.