On the Mechanism of Carbohydroxypalladation of Enynes. Additional Insights on the Cyclization of Enynes with Electrophilic Metal Complexes

Cristina Nevado, Lise Charruault, Véronique Michelet, Cristina Nieto-Oberhuber, Maria Munoz-Herranz, María Méndez, Marie-Noëlle Rager, Jean-Pierre Genêt, Antonio M. Echavarren

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Abstract

Different mechanisms have been proposed for the cyclization of enynes catalyzed by electrophilic metal halides or complexes. We present evidence to indicate that the previously reported “carbohydroxypalladation” and the “hydroxycyclization catalyzed by PtII” are closely related reactions. Thus, palladium complexes formed in situ from PdCl2 and trisulfonated phosphane TPPTS or cyclic phosphite P(OCH2)3CEt as the ligands catalyze the methoxy- or hydroxycyclization of enynes with selectivities similar to those observed with PtII complexes. Deuteration studies indicate that activation of the alkyne by PdII promotes an anti-addition of the alkene.
Original languageEnglish
Pages (from-to)706-713
Number of pages8
JournalEuropean Journal of Organic Chemistry
Volume2003
Issue number4
DOIs
Publication statusPublished - 2003

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