Copper–Carbene Intermediates in the Copper‐Catalyzed Functionalization of OH Bonds. Issue 27 (26th May 2015)

• Record Type: Journal Article
• Authors: Pereira, Ana; Champouret, Yohan; Martín, Carmen; Álvarez, Eleuterio; Etienne, Michel; Belderraín, Tomás R.; Pérez, Pedro J.
• Is Part Of: Chemistry. Volume 21:Issue 27(2015)
• Page Start: 9769
• Page End: 9775
• Publication Date: 2015-05-26
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201500776
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Copper–carbene [Tp^{<italic>x</italic>}CuC(Ph)(CO₂Et)] and copper–diazo adducts [Tp^{<italic>x</italic>}Cu{η¹‐N₂C(Ph)(CO₂Et)}] have been detected and characterized in the context of the catalytic functionalization of OH bonds through carbene insertion by using N₂C(Ph)(CO₂Et) as the carbene source. These are the first examples of these type of complexes in which the copper center bears a tridentate ligand and displays a tetrahedral geometry. The relevance of these complexes in the catalytic cycle has been assessed by NMR spectroscopy, and kinetic studies have demonstrated that the N‐bound diazo adduct is a dormant species and is not en route to the formation of the copper–carbene intermediate.</p> </abstract>