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Palladium-catalyzed decarboxylative rearrangements of allyl 2,2,2-trifluoroethyl malonates: direct access to homoallylic esters.

ABSTRACT: Homoallylic esters are obtained in a single transformation from allyl 2,2,2-trifluoroethyl malonates by using a Pd(0) catalyst. Facile decarboxylation of allyl 2,2,2-trifluoroethyl malonates is attributed to a decrease in pK(a) compared to allyl methyl malonates. Subsequent reduction of the homoallylic 2,2,2-trifluoroethyl ester provides a (hydroxyethyl)cyclopentenyl derivative that represents a key intermediate in the synthesis of carbocyclic nucleosides. A select allyl 2,2,2-trifluoroethyl malonate undergoes a decarboxylative Claisen rearrangement to provide a regioisomeric homoallylic ester.

SUBMITTER: Tardibono LP

PROVIDER: S-EPMC2767373 | biostudies-literature | 2009 Sep

REPOSITORIES: biostudies-literature

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Palladium-catalyzed decarboxylative rearrangements of allyl 2,2,2-trifluoroethyl malonates: direct access to homoallylic esters.

Tardibono Lawrence P LP Patzner Jerod J Cesario Cara C Miller Marvin J MJ

Organic letters 20090901 18

Homoallylic esters are obtained in a single transformation from allyl 2,2,2-trifluoroethyl malonates by using a Pd(0) catalyst. Facile decarboxylation of allyl 2,2,2-trifluoroethyl malonates is attributed to a decrease in pK(a) compared to allyl methyl malonates. Subsequent reduction of the homoallylic 2,2,2-trifluoroethyl ester provides a (hydroxyethyl)cyclopentenyl derivative that represents a key intermediate in the synthesis of carbocyclic nucleosides. A select allyl 2,2,2-trifluoroethyl mal ...[more]

PMID: 19694457

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