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Intertwined Analytical, Experimental and Theoretical Studies on the Formation and Structure of a Copper Dienolate
Author(s) -
Lecachey Baptiste,
Palais Laetitia,
Courcy Benoît,
Bouauli Samira,
Durandetti Muriel,
Oulyadi Hassan,
HarissonMarchand Anne,
Maddaluno Jacques,
Gérard Hélène,
Vrancken Emmanuel,
Campagne JeanMarc
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202100596
Subject(s) - copper , catalysis , chemistry , salt (chemistry) , crystallography , organic chemistry
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.