Aerobic Aliphatic Hydroxylation Reactions by Copper Complexes: A Simple Clip-and-Cleave Concept

Chemistry : a European Journal
Jonathan BeckerSiegfried Schindler

Abstract

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(CH3 CN)4 ][CF3 SO3 ]. After exposure of the reaction mixture to dioxygen acidic cleavage and aqueous workup liberates the corresponding β-hydroxylated aldehyde. The concept for the hydroxylation of trimethylacetaldehyde as well as adamantane and diamantane 1-carbaldehydes was investigated and the corresponding β-hydroxy aldehydes were obtained with high selectivities. The results of low temperature stopped-flow measurements indicate the formation of a bis(μ-oxido)dicopper complex as reactive intermediate. According to density functional theory (DFT, RI-BLYP-D3/def2-TZVP(SDD)/ COSMO(CH2 Cl2 )//RI-PBE-D3/def2-TZVP(SDD)) computations CH bonds suitably predisposed to the [Cu2 O2 ]2+ core undergo hydroxylation in a concerted step with particularly low activation barriers, which explains the experimentally observed regioselectivities.

References

Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Dec 14, 1999·Angewandte Chemie·T WistubaP Kircher
Jul 24, 2003·Angewandte Chemie·Bruno SchöneckerHelmar Görls
Dec 18, 2003·Angewandte Chemie·Philipp Spuhler, Max C Holthausen
Feb 12, 2004·Chemical Reviews·Liviu M MiricaT Daniel P Stack
Feb 12, 2004·Chemical Reviews·Elizabeth A Lewis, William B Tolman
Sep 7, 2005·Chemistry : a European Journal·Joseph A WrightJonathan B Spencer
Dec 22, 2005·Journal of the American Chemical Society·Sara PalaviciniLuigi Casella
Apr 1, 2006·Trends in Biotechnology·Sergio Riva
Apr 25, 2006·Physical Chemistry Chemical Physics : PCCP·Florian Weigend
Mar 4, 2011·Journal of Computational Chemistry·Stefan GrimmeLars Goerigk
Jun 26, 2012·Critical Reviews in Biochemistry and Molecular Biology·Megen A Culpepper, Amy C Rosenzweig
Jun 22, 2013·Chemical Reviews·Scott E AllenMarisa C Kozlowski
Oct 1, 2014·The Journal of Organic Chemistry·Anastasiya V BarabashAndrey A Fokin
Jun 20, 2015·Chemistry : a European Journal·Jonathan BeckerSiegfried Schindler
Oct 16, 2015·Journal of the American Chemical Society·Yi Yang SeePhil S Baran
Dec 7, 2016·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·David A QuistKenneth D Karlin
Jan 20, 2017·Chemical Reviews·Courtney E ElwellWilliam B Tolman
Feb 13, 2017·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Lawrence Que
Jun 28, 2017·The Journal of Organic Chemistry·Rachel TrammellIsaac Garcia-Bosch
Mar 1, 2018·Chemistry : a European Journal·Marta LarrosaRadim Hrdina

❮ Previous
Next ❯

Citations

May 28, 2019·Chemistry : a European Journal·Florian SchönHans-Jörg Himmel
Aug 6, 2021·Journal of Inorganic Biochemistry·Shuming ZhangIsaac Garcia-Bosch
May 16, 2019·Inorganic Chemistry·Rachel TrammellIsaac Garcia-Bosch

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.