Regiochemical control in the Pd(II)-catalyzed Claisen rearrangement via in situ enol ether exchange

Tetrahedron Letters

Volumn 37, Issue 44, 1996, Pages 7991-7994

  Sugiura, Masaharu ^a   Nakai, Takeshi ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

KETONE;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; REACTION ANALYSIS; STEREOCHEMISTRY; TECHNIQUE;

EID: 0030605147     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)01790-X     Document Type: Article

References (22)

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4. 2. (a) Baan, J. L.; Bickelhaupt, F. Tetrahedron Lett. 1986, 27, 6267-6270.
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12. 4. (a) Daub, G. W.; Sanchez, M. G.; Cromer, R. A.; Gibson, L. L. J. Org. Chem. 1982, 47, 743-745.
13. (b) Daub, G. W.; McCoy, M. A.; Sanchez, M. G.; Carter, J. S. J. Org. Chem. 1983, 48, 3876-3883.
14. (c) Daub, G. W.; Lunt, S. R. Tetrahedron Lett. 1983, 24, 4397-4400.
15. (d) Grattan, T. J.; Whitehurst, J. S. J. Chem. Soc. Perkin Trans. 1 1990, 11-18.
16. 5. Rychnovsky, S. D.; Lee, J. L. J. Org. Chem. 1995, 60, 4318-4319.
17. 6. The regioisomeric mixture of 1a was prepared from 2-methylcyclohexanone according to the reported procedure: Wohl, R. A. Synthesis 1974, 38-40.
18. 13C NMR 12.6, 20.0, 20.7, 21.1, 27.1, 35.5, 39.4, 49.8, 52.1, 117.0, 137.5, 215.3.
19. 2,3-1a once separated gave essentially the same regiochemical outcome.
20. 9. The enol allylic ethers concerned are likely to form reversibly via an alcohol addition to 1a followed by an alcohol elimination from the acetal thus formed.
21. 10. The enol methyl ethers 1b and 1c were prepared following the literature procedure: Okazoe, T.; Takai, K.; Oshima, K.; Utimoto, K. J. Org. Chem. 1987, 52, 4410-4412.
22. 3c,d which is stericallyless congested than the boat-like counterpart (equation presented)