- Palladium(0)-Catalyzed Alkoxycarbonylation of Allyl Phosphates and Acetates
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Palladium-catalyzed alkoxycarbonylation of allyl phosphates under CO (1 atm) at 50 deg C proceeds highly efficiently to give the corresponding β,γ-unsaturated esters.The carbonylation of geranyl phosphate ((E)-11) under CO (1 atm) at 50 deg C gave ethyl ester of homogeranic acid ((E)-12) stereoselectively.The carbonylation takes place at least substituted allylic positions with inversion of configuration.Typically, the methoxycarbonylation of cis-5-(methoxycarbonyl)-2-cyclohexen-1-yl phosphate (cis-16) gave trans-dimethyl-2-cyclohexene-1,5-dicarboxylate (trans-17) selectively.Alkoxycarbonylation of allyl acetates is performed for the first time in the presence of a catalytic amount of bromide ion.The reaction can be rationalized by assuming the mechanism which involves oxidative addition of palladium(0) species to allyl acetates to give ?-allylpalladium acetate, fast ligand exchange of the acetate with bromide, insertion of carbon monoxide to give acylpalladium species, and alkoxylation.
- Murahashi, Shun-Ichi,Imada, Yasushi,Taniguchi, Yuki,Higashiura, Shinya
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p. 1538 - 1545
(2007/10/02)
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- PALLADIUM(O)-CATALYZED CARBONYLATION OF ALLYL PHOSPHATES AND ALLYL ACETATES. SELECTIVE SYNTHESIS OF β,γ-UNSATURATED ESTERS.
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Palladium catalyzed carbonylations of allyl phosphates and allyl acetates give β,γ-unsaturated esters efficiently.The latter reaction requires bromide ion as a co-catalyst.
- Murahashi, Shun-Ichi,Imada, Yasushi,Taniguchi, Yuki,Higashiura, Shin-ya
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p. 4945 - 4948
(2007/10/02)
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