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Chiral tetranuclear and dinuclear copper(II) complexes for TEMPO-mediated aerobic oxidation of alcohols : are four metal centres better than two?

Zhang, G. and Proni, G. and Zhao, S. and Constable, E. C. and Housecroft, C. E. and Neuburger, M. and Zampese, J. A.. (2014) Chiral tetranuclear and dinuclear copper(II) complexes for TEMPO-mediated aerobic oxidation of alcohols : are four metal centres better than two? Dalton transactions, 43 (32). pp. 12313-12320.

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Abstract

The one-pot reaction of 3,5-di-tert-butyl-2-hydroxybenzaldehyde, (R)-2-aminoglycinol and Cu(OAc)2·2H2O in a 1 : 1 : 1 ratio in the presence of triethylamine led to the isolation of X-ray quality crystals of the chiral complex (R)-1 in high yield. The single crystal structure of (R)-1 reveals a tetranuclear copper(II) complex that contains a {Cu4(μ-O)2(μ3-O)2N4O4} core. A reaction using (1S,2R)-2-amino-1,2-diphenylethanol as precursor under the same conditions generated the chiral complex (S,R)-2; its structure was determined by single crystal X-ray crystallography and was found to contain a {Cu2(μ-O)2N2O2} core. Both (R)-1 and (S,R)-2 have been used for catalytic aerobic oxidation of benzylic alcohols in combination with the TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl) radical. (R)-1 selectively catalyses the conversion of various aromatic primary alcohols to the corresponding aldehydes with high yields (99%) and TONs (770) in the air, while (S,R)-2 exhibits less promising catalytic performance under the same reaction conditions. The role of the cluster structures in (R)-1 and (S,R)-2 in controlling the reactivity towards aerobic oxidation reactions is discussed.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Constable)
05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Housecroft)
UniBasel Contributors:Housecroft, Catherine Elizabeth and Constable, Edwin Charles and Neuburger, Markus and Zampese, Jennifer Ann
Item Type:Article, refereed
Bibsysno:Link to catalogue
Publisher:Royal Society of Chemistry
ISSN:1477-9226
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:31 Dec 2015 10:56
Deposited On:10 Oct 2014 09:19

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