The Pd(II)-catalyzed and the thermal claisen rearrangement of 2- alkoxycarbonyl-substituted allyl vinyl ethers

Synlett

Volumn , Issue 11, 1999, Pages 1823-1825

  Hiersemann, Martin ^a  

^a NONE

Author keywords

Catalysis; Diastereo selectivity; Esters; Palladium; Rearrangement

Indexed keywords

ALLYL COMPOUND; ESTER DERIVATIVE; ETHER DERIVATIVE; PALLADIUM; VINYL DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; DIASTEREOISOMER; HEATING; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS; TEMPERATURE SENSITIVITY;

EID: 0032704418     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1999-2932     Document Type: Article

References (23)

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12. Hiersemann, M. Tetrahedron 1999, 55, 2625.
13. Double bond configuration was assigned based on NOESY experiments.
14. For examples of the thermal Claisen rearrangement of acyclic 2-alkoxycarbonyl-substituted allyl vinyl ethers, see (a) Hase, T. A.; Ourila, A., Holmberg, C. J. Org. Chem. 1981, 46, 3137.
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19. 3= 9.9 Hz). This observation is consistent for a number of structurally related α-keto esters which we have synthesized.
20. A reaction time of 4 h led to a (Z,E)-2a:(E,E)-2a:anti-3a= 60:7:33 ratio (91 % isolated yield). On the other hand, stirring for 48 h afforded the same ratio as was obtained after 24 h.
21. 4 (256.3): calcd. C 66.64, H 9.15; found C 66.75, H 9.10.
22. For a discussion of the possible mechanism of the Pd(II)-catalyzed Claisen rearrangement, see reference 5.
23. 2.