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

doi:10.1002/ejoc.200390110

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

Chemistry of Materials and Catalysis

Research output: Contribution to journal › Article › peer-review

108 Citations (Scopus)

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 Pt^II” 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 Pt^II complexes. Deuteration studies indicate that activation of the alkyne by Pd^II promotes an anti-addition of the alkene.

Original language	English
Pages (from-to)	706-713
Number of pages	8
Journal	European Journal of Organic Chemistry
Volume	2003
Issue number	4
Early online date	23 Jan 2003
DOIs	https://doi.org/10.1002/ejoc.200390110
Publication status	Published - Feb 2003

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10.1002/ejoc.200390110

Cite this

Nevado, C., Charruault, L., Michelet, V., Nieto-Oberhuber, C., Munoz-Herranz, M., Méndez, M., Rager, M-N., Genêt, J-P., & Echavarren, A. M. (2003). On the mechanism of carbohydroxypalladation of enynes. Additional insights on the cyclization of enynes with electrophilic metal complexes. European Journal of Organic Chemistry, 2003(4), 706-713. https://doi.org/10.1002/ejoc.200390110

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title = "On the mechanism of carbohydroxypalladation of enynes. Additional insights on the cyclization of enynes with electrophilic metal complexes",

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.",

author = "Cristina Nevado and Lise Charruault and V{\'e}ronique Michelet and Cristina Nieto-Oberhuber and Maria Munoz-Herranz and Mar{\'i}a M{\'e}ndez and Marie-No{\"e}lle Rager and Jean-Pierre Gen{\^e}t and Echavarren, {Antonio M.}",

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Nevado, C, Charruault, L, Michelet, V, Nieto-Oberhuber, C, Munoz-Herranz, M, Méndez, M, Rager, M-N, Genêt, J-P & Echavarren, AM 2003, 'On the mechanism of carbohydroxypalladation of enynes. Additional insights on the cyclization of enynes with electrophilic metal complexes', European Journal of Organic Chemistry, vol. 2003, no. 4, pp. 706-713. https://doi.org/10.1002/ejoc.200390110

TY - JOUR

T1 - On the mechanism of carbohydroxypalladation of enynes. Additional insights on the cyclization of enynes with electrophilic metal complexes

AU - Nevado, Cristina

AU - Charruault, Lise

AU - Michelet, Véronique

AU - Nieto-Oberhuber, Cristina

AU - Munoz-Herranz, Maria

AU - Méndez, María

AU - Rager, Marie-Noëlle

AU - Genêt, Jean-Pierre

AU - Echavarren, Antonio M.

PY - 2003/2

Y1 - 2003/2

N2 - 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.

AB - 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.

U2 - 10.1002/ejoc.200390110

DO - 10.1002/ejoc.200390110

M3 - Article

VL - 2003

SP - 706

EP - 713

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

SN - 1434-193X

IS - 4

ER -