Abstract

The triethylborane-promoted and palladium-catalyzed reactions of 2,4-dienyl alcohols or the corresponding isomeric divinyl alcohols with bis(trifluoroethyl) malonates provide an improved method for the regio- and stereoselective dienylation of malonates. The phosphine ligand is an important control element in the reaction. Combinations of Pd(OAc) 2 with BIPHEP or BINAP give dienylated malonates in good yield and higher isomeric purity than the traditional combination of Pd(OAc) 2 and Ph 3P affords in the catalyzed reactions of dienyl acetates.

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