Dynamic chirality of (E)-5-cyclononen-1-one and its enolate

Journal of the American Chemical Society

Volumn 133, Issue 6, 2011, Pages 1754-1756

  Tomooka, Katsuhiko ^a   Ezawa, Takayuki ^b   Inoue, Hiroko ^a   Uehara, Kazuhiro ^a   Igawa, Kazunobu ^a  

^a KYUSHU UNIVERSITY   (Japan)

^b TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CHIRAL NUCLEOPHILES; DYNAMIC CHIRALITY; ENOLATES; PLANAR CHIRALITY; TOPOLOGICAL CONSTRAINTS;

CHIRALITY; ENANTIOMERS; STEREOCHEMISTRY;

ENZYMATIC HYDROLYSIS;

5 CYCLONONEN 1 ONE; ENZYME; KETONE DERIVATIVE; NUCLEOPHILE; UNCLASSIFIED DRUG;

ARTICLE; CHIRALITY; ENANTIOMER; HYDROLYSIS;

EID: 79951520359     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja1092375     Document Type: Article

References (39)

1. Patai, S., Ed. The Chemistry of the Carbonyl Group; Interscience: New York, 1966.
2. Zabicky, J., Ed. The Chemistry of the Carbonyl Group; Interscience: New York, 1970; Vol. 2.
3. Müller, E., Ed. Methoden der Organischen Chemie (Houben-Weyl) [Methods of Organic Chemistry], 4 th ed.; Thieme: Stuttgart, 1973; Vol. 7/2a.
4. Müller, E., Ed. Methoden der Organischen Chemie (Houben-Weyl) [Methods of Organic Chemistry], 4 th ed.; Thieme: Stuttgart, 1976; Vol. 7/2b.
5. Müller, E., Ed. Methoden der Organischen Chemie (Houben-Weyl) [Methods of Organic Chemistry], 4 th ed.; Thieme: Stuttgart, 1977; Vol. 7/2c.
6. For reviews, see Marshall, J. A. Acc. Chem. Res. 1980, 13, 213-218
7. Nakazaki, M.; Yamamoto, K.; Naemura, K. Top. Curr. Chem. 1984, 125, 1-25
8. Schlögl, K. Top. Curr. Chem. 1984, 125, 27-62
9. Eliel, E. L.; Wilen, S. H.; Mander, L. N. Stereochemistry of Organic Compounds; Wiley: New York, 1994; pp 1172 - 1175.
10. Cope, A. C.; Ganellin, C. R.; Johnson, H. W., Jr.; Auken, T. V. V.; Winkler, H. J. S. J. Am. Chem. Soc. 1963, 85, 3276-3279
11. Cope, A. C.; Pawson, B. A. J. Am. Chem. Soc. 1965, 87, 3649-3651
12. Cope, A. C.; Banholzer, K.; Keller, H.; Pawson, B. A.; Whang, J. J.; Winkler, H. J. S. J. Am. Chem. Soc. 1965, 87, 3644-3649
13. -1 by Hoppes group; see Deiters, A.; Mück-Lichtenfeld, C.; Fröhlich, R.; Hoppe, D. Chem.-Eur. J. 2002, 8, 1833-1842
14. We have reported that heterocycle congeners of 4 have stable planar chirality at ambient temperature; see Tomooka, K.; Komine, N.; Fujiki, D.; Nakai, T.; Yanagitsuru, S. J. Am. Chem. Soc. 2005, 127, 12182-12183
15. Tomooka, K.; Suzuki, M.; Shimada, M.; Yanagitsuru, S.; Uehara, K. Org. Lett. 2006, 8, 963-965
16. Uehara, K.; Tomooka, K. Chem. Lett. 2009, 38, 1028-1029
17. Ketone 2a has been reported by two groups already; however, its stereochemical behavior has not yet been reported. Lange, G. T.; Hall, T.-W. J. Org. Chem. 1974, 39, 3819-3822
18. Kato, T.; Kondo, H.; Nishino, M.; Tanaka, M.; Hata, G.; Miyake, A. Bull. Chem. Soc. Jpn. 1980, 53, 2958-2961
19. Owing to the symmetric structure of 2a, only one regioisomer of 3 is present.
20. It is known that the length of the C - C bond of enol ether is nearly identical to that of simple alkene; see Samdal, S.; Seip, H. M. J. Mol. Struct. 1975, 28, 193-203 Therefore, it can be anticipated that the rigidity of the ring conformation, and hence the stereochemical stability of 3, would be at a level similar to that of 4
21. The generation and synthetic application of dynamic chiral enolate from α-chiral ketone has been reported by Fuji and Kawabatas group; see Kawabata, T.; Yahiro, K.; Fuji, K. J. Am. Chem. Soc. 1991, 113, 9694-9696
22. Fuji, K.; Kawabata, T. Chem.-Eur. J. 1998, 4, 373-376 and references cited therein
23. Kato and coworkers originally synthesized 2a in 60% yield by a thermal oxy-Cope rearrangement of 5a; see ref 7b. A similar transformation by anionic oxy-Cope rearrangement provides a rather high yield of 2a (86%). For a review of a ring-enlarging oxy-Cope rearrangement, see Paquette, L. A. Angew. Chem., Int. Ed. Engl. 1990, 29, 609-626
24. Analytical HPLC and GC: CHIRALPAK AS-H (4.6 mm × 250 mm) for 2a, 2b, 2d; CHIRALPAK AD-H (4.6 mm × 250 mm) for 3a - d; CHIRALCEL OD-H (4.6 mm × 250 mm) for 2c, 6; SUPELCO ?-DEX 225 (0.25 mm × 30 m) for 9; see Supporting Information for details.
25. -1 for 2a, 2b, and 3a, respectively; see Supporting Information for details.
26. Determination of the absolute stereochemistry of 2a itself was difficult, owing to its stereochemical instability at ambient temperature and noncrystallinity.
27. 2(2,4,6-trimethylpyridine) complex of planar chiral nitrogencycles. Tomooka, K.; Shimada, M.; Uehara, K.; Ito, M. Organometallics 2010, 29, 6632-6635
28. The structures of 6 and 7a were determined by X-ray crystallography; see Supporting Information.
29. Stereochemical stabilizing effect of dimethyl substituent in (E)-cyclodecene system has been reported; see Marshall, J. A.; Konicek, T. R.; Flynn, K. E. J. Am. Chem. Soc. 1980, 102, 3287-3288
30. By comparison of activation parameters for the racemization, a stereochemical stability of 3a lies between those of compounds 1 and 4 (ref 5).
31. 2(2,4,6-trimethylpyridine) complex derivative; see Supporting Information for details.
32. Silyl enol ether congener of 3 has been synthesized; see Kende, A. S.; Nelson, C. E. M.; Fuchs, S. Tetrahedron Lett. 2005, 46, 8149-8152 However, its stereochemical behavior has not been reported.
33. Enzyme-mediated asymm.hydrolysis of prochiral or α-chiral enolates has been reported; see Matsumoto, K.; Ohta, H. Chem. Lett. 1989, 1109-1112
34. Matsumoto, K.; Tsutsumi, S.; Ihori, T.; Ohta, H. J. Am. Chem. Soc. 1990, 112, 9614-9619
35. We measured the conversion yields by HPLC analysis. The enantiopurity of ketone 2a was not determined due to its rapid racemization. We also performed a 100-mg-scale reaction and isolated an enantioenriched 3a in 32% yield with >96% ee; see Supporting Information for details.
36. We have observed a rapid epimerization of 8 in terms of planar chirality at ambient temperature.
37. This result also shows that interconversion of enolates 3 (Y = Ac ? Li) under these conditions proceeds without loss of enantiopurity.
38. rac-8 and rac-9 have been synthesized and ulitized as a precursor of rac-phoracantholide I by Baldwins group; see Baldwin, J. E.; Adlington, R. M.; Singh, R. Tetrahedron 1992, 48, 3385-3412
39. (R)- 9 has been synthesized and ulitized as a precursor of (R)-(-)-phoracantholide I by Enderss group; see Enders, D.; Plant, A.; Drechsel, K.; Prokopenko, O. F. Liebigs Ann. 1995, 1127-1128