Journal article
Authors list: Becker, J; Zhyhadlo, YY; Butova, ED; Fokin, AA; Schreiner, PR; Förster, M; Holthausen, MC; Specht, P; Schindler, S
Publication year: 2018
Pages: 15543-15549
Journal: Chemistry - A European Journal
Volume number: 24
Issue number: 58
ISSN: 0947-6539
DOI Link: https://doi.org/10.1002/chem.201802607
Publisher: Wiley
A simple imine clip-and-cleave concept has been developed for the selective hydroxylation of non-activated CH bonds in aliphatic aldehydes with dioxygen through a copper complex. The synthetic protocol involves reaction of a substrate aldehyde with N,N-diethyl-ethylendiamine to give the corresponding imine, which is used as a bidentate donor ligand forming a copper(I) complex with [Cu(CH3CN)(4)][CF3SO3]. After exposure of the reaction mixture to dioxygen acidic cleavage and aqueous workup liberates the corresponding beta-hydroxylated aldehyde. The concept for the hydroxylation of trimethylacetaldehyde as well as adamantane and diamantane 1-carbaldehydes was investigated and the corresponding beta-hydroxy aldehydes were obtained with high selectivities. The results of low temperature stopped-flow measurements indicate the formation of a bis(mu-oxido)dicopper complex as reactive intermediate. According to density functional theory (DFT, RI-BLYP-D3/def2-TZVP(SDD)/COSMO(CH2Cl2)//RI-PBE-D3/def2-TZVP(SDD)) computations CH bonds suitably predisposed to the [Cu2O2](2+) core undergo hydroxylation in a concerted step with particularly low activation barriers, which explains the experimentally observed regioselectivities.
Abstract:
Citation Styles
Harvard Citation style: Becker, J., Zhyhadlo, Y., Butova, E., Fokin, A., Schreiner, P., Förster, M., et al. (2018) Aerobic Aliphatic Hydroxylation Reactions by Copper Complexes: a Simple Clip-and-Cleave Concept, Chemistry - A European Journal, 24(58), pp. 15543-15549. https://doi.org/10.1002/chem.201802607
APA Citation style: Becker, J., Zhyhadlo, Y., Butova, E., Fokin, A., Schreiner, P., Förster, M., Holthausen, M., Specht, P., & Schindler, S. (2018). Aerobic Aliphatic Hydroxylation Reactions by Copper Complexes: a Simple Clip-and-Cleave Concept. Chemistry - A European Journal. 24(58), 15543-15549. https://doi.org/10.1002/chem.201802607