Palladium-catalyzed decarboxylative rearrangements of allyl 2,2,2-trifluoroethyl malonates: direct access to homoallylic esters.
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.
Tardibono
Lawrence P
LP
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA.
Patzner
Jerod
J
Cesario
Cara
C
Miller
Marvin J
MJ
D002384:Catalysis; D003500:Cyclization / Q000528:radiation effects; D003653:Decarboxylation / Q000187:drug effects; D008314:Malonates / Q000737:chemistry*; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*
D008314:Malonates; D010165:Palladium; C005230:methyl malonate
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