ISSN:
1434-193X
Keywords:
Homogeneous catalysis
;
Palladium
;
Acetoxylation
;
Acryloxylation
;
Addition reactions
;
Cyclooctadiene
;
Cyclooct-4-enone
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
---Palladium-catalyzed acryloxylation of several cycloalkenes in the presence of the Pd(OAc)2/p-benzoquinone/MnO2 catalytic system is reported. This oxidation reaction yields allylic acrylates as the sole products through the intermediacy of an η3-allyl complex. However, with 1,5-cyclooctadiene (3), cyclooct-4-enone (4) is the major reaction product. Its formation results from oxidation, which is also observed in the palladium-catalyzed acetoxylation of 3. It has been shown that this is the result of a 1,2-trans addition (acryloxy-palladation), followed by a β-hydride elimination, which yields an enol acrylate or acetate. A second Markovnikov-oriented 1,2-trans-acryloxy-palladation on the latter yields a palladium complex, rearrangement of which gives 4.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
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