Buchumschlag

Structural and mechanistic studies of the copper(II)-assisted ortho-hydroxylation of benzoates by trimethylamine N-oxide

N-benzoyl-2-methylalanine (H2L1) is ortho-hydroxylated stereoselectively by trimethylamine N-oxide (TMAO) in the presence of copper(II). The experimental structure of [Cu(L1)(TMAO)2] suggests that the oxygen transfer agent TMAO transfers the oxygen atom to copper(II), and (L1)2−, coordinated to copp...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Hauptverfasser: Bujis, Wim (VerfasserIn) , Comba, Peter (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 2002
In: Journal of organometallic chemistry
Year: 2002, Jahrgang: 641, Heft: 1/2, Pages: 71-80
ISSN:1872-8561
DOI:10.1016/S0022-328X(01)01291-8
Online-Zugang:Verlag, Pay-per-use, Volltext: http://dx.doi.org/10.1016/S0022-328X(01)01291-8
Verlag, Pay-per-use, Volltext: http://www.sciencedirect.com/science/article/pii/S0022328X01012918
Volltext
Verfasserangaben:Wim Buijs, Peter Comba, Danny Corneli, Hans Pritzkow
Beschreibung
Zusammenfassung:N-benzoyl-2-methylalanine (H2L1) is ortho-hydroxylated stereoselectively by trimethylamine N-oxide (TMAO) in the presence of copper(II). The experimental structure of [Cu(L1)(TMAO)2] suggests that the oxygen transfer agent TMAO transfers the oxygen atom to copper(II), and (L1)2−, coordinated to copper(II) by a carboxylate oxygen and the amide nitrogen donor, is well pre-organized for an oxygen transfer from copper to the ortho carbon atom of the benzene ring. Product analyses as a function of reaction time of the copper(II)-mediated ortho-hydroxylation reaction with H2L1 and various derivatives support the suggestion of a reactive copper-oxo or copper-hydroxo intermediate, stabilized by a five-membered chelate with hard carboxylate and N-amide donors. The analysis also suggests that there is a pre-equilibrium with a Cu:L=1:1 ratio, and this might involve Cu/L2−/TMAO or dicopper complexes. Depending on the ligand H2L, complexation with the salicylate product may inhibit the ortho-hydroxylation reaction.
Beschreibung:Gesehen am 06.03.2018
Article was first available online on 14 December 2001
Beschreibung:Online Resource
ISSN:1872-8561
DOI:10.1016/S0022-328X(01)01291-8

Ähnliche Einträge