Intertwined Analytical, Experimental and Theoretical Studies on the Formation and Structure of a Copper Dienolate

Intertwined Analytical, Experimental and Theoretical Studies on the Formation and Structure of a Copper Dienolate

The reaction of a silyl dienolate, a Cu(II) salt and TBAT yielding the corresponding copper dienolate is addressed. A combined NMR and cyclic voltammetry analysis first highlight the role of TBAT in the Cu(II) to Cu(I) reduction and the structure of the precatalytic species. From these first results...

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Bibliographic Details
Published in:Chemistry : a European journal Vol. 27; no. 29; pp. 7942 - 7950
Main Authors: Lecachey, Baptiste, Palais, Laetitia, Courcy, Benoît, Bouauli, Samira, Durandetti, Muriel, Oulyadi, Hassan, Harisson‐Marchand, Anne, Maddaluno, Jacques, Gérard, Hélène, Vrancken, Emmanuel, Campagne, Jean‐Marc
Format: Journal Article
Language:English
Published: Germany Wiley Subscription Services, Inc 20-05-2021
Wiley-VCH Verlag
Subjects:
ab initio calculations
Catalysts
Chemical Sciences
Chemistry
Copper
copper dienolate
NMR
Nuclear magnetic resonance
reaction mechanisms
silyl dienolate
structure elucidation
reaction mechanisms
copper dienolate
ab initio calculations
structure elucidation
silyl dienolate
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Summary:The reaction of a silyl dienolate, a Cu(II) salt and TBAT yielding the corresponding copper dienolate is addressed. A combined NMR and cyclic voltammetry analysis first highlight the role of TBAT in the Cu(II) to Cu(I) reduction and the structure of the precatalytic species. From these first results a second set of NMR and theoretical studies enable the determination of the structure and the mechanism of formation of the copper dienolate catalytic species. Finally, we showed that that the copper catalyst promote the E/Z s‐cis/s‐trans equilibration of the silyl dienolate precursor through a copper dienolate intermediate. All of these results unveil some peculiarities of the catalytic and asymmetric vinylogous Mukaiyama reaction. An intertwined analytical, experimental and theoretical study disclose the mechanism of formation of an organocopper dienolate reagent from its silylated precursor. The study shed light on the Cu(II) to Cu(I) reduction process, the Si to Cu exchange mechanism and finally the metallotropic equilibrium of the resulting copper dienolate.
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ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202100596