Activation of the C-H bond by electrophilic attack: theoretical study of the reaction mechanism of the aerobic oxidation of alcohols to aldehydes by the Cu(bipy)(2+)/2,2,6,6-tetramethylpiperidinyl-1-oxy cocatalyst system

Inorganic Chemistry
Carine MichelEvert Jan Baerends

Abstract

We have investigated the reaction mechanism of the selective aerobic oxidation of primary alcohols into aldehydes using a bipy-copper complex and the 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) radical as cocatalysts (Gamez et al. Chem. Commun. 2003, 2412-2415) and compared it to the well-known oxidation by the TEMPO(+) ion. Our theoretical investigation shows that (a) the oxidation of alcohols to aldehydes by uncoordinated TEMPO(+) takes place by electrophilic attack on the C-H(alpha) bond of the alcohol; (b) the Cu(bipy)(2+) complex has two functions, namely, (1) it acts as a template that brings TEMPO and the (deprotonated) alcohol in proximity by coordinating these moieties in adjacent coordination sites, and (2) it oxidizes the TEMPO radical to (coordinated) TEMPO(+) ion. The H abstraction from alcohol by TEMPO(+) then proceeds as an intramolecular reaction, very much analogous to one of the reaction pathways with free TEMPO(+) and with a remarkably low barrier. We stress that compared to other A-H bonds (A = C, N, O, F), the relatively high-lying C-H bonds are particularly susceptible to electrophilic attack, and notably the C-H(alpha) bond next to the O in an alcohol is so because it is pushed up by an O lone pair. Elec...Continue Reading

References

Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Oct 7, 2003·Organic & Biomolecular Chemistry·Arné DijksmanRoger A Sheldon
Nov 1, 2003·Chemical Communications : Chem Comm·Patrick GamezRoger A Sheldon
Jun 9, 2005·Chemical Reviews·Sason ShaikWalter Thiel
Jul 13, 2006·The Journal of Physical Chemistry. a·André R GroenhofKoop Lammertsma
Dec 14, 2006·Physical Chemistry Chemical Physics : PCCP·Manuel J Louwerse, Evert Jan Baerends
May 10, 2007·The Journal of Organic Chemistry·William F BaileyKenneth B Wiberg

❮ Previous
Next ❯

Citations

Nov 5, 2011·Inorganic Chemistry·Paola BelanzoniEvert Jan Baerends
Jul 9, 2010·Journal of the American Chemical Society·Jeffrey F Van HumbeckDavid W C MacMillan
Dec 3, 2010·Journal of the American Chemical Society·Susan K HansonDavid L Thorn
Aug 25, 2011·Journal of the American Chemical Society·Jessica M Hoover, Shannon S Stahl
Nov 9, 2012·Journal of the American Chemical Society·Jeremiah J ScepaniakTrevor W Hayton
Jan 16, 2013·Journal of the American Chemical Society·Jessica M HooverShannon S Stahl
Jul 4, 2013·Journal of the American Chemical Society·Justin P LomontCharles B Harris
Dec 19, 2012·The Journal of Organic Chemistry·Monissa C PaderesSherry R Chemler
Feb 10, 2016·Journal of the American Chemical Society·Keisuke TokumasuTakashi Ohshima
Dec 24, 2015·Journal of the American Chemical Society·Scott D McCann, Shannon S Stahl
Feb 26, 2016·Journal of the American Chemical Society·Ellen C HayesStefan Stoll
Apr 5, 2016·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Manas SutradharArmando J L Pombeiro
Oct 16, 2016·The Journal of Organic Chemistry·Scott W KrabbeJustin A Simanis
Aug 5, 2014·Journal of the American Chemical Society·Bradford L RylandShannon S Stahl
Mar 29, 2014·Chemical Communications : Chem Comm·Qun CaoMark J Muldoon
May 7, 2020·Chemistry, an Asian Journal·Susanta HazraAnil J Elias
Dec 14, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Ramachandran AzhakarDietmar Stalke
Aug 16, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Oindrila Das, Tapan Kanti Paine
Nov 20, 2016·Chemistry : a European Journal·Mark A Iron, Alex M Szpilman
Oct 24, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Manas SutradharArmando J L Pombeiro
Jan 24, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Zhen MaArmando J L Pombeiro
Nov 24, 2020·Organic & Biomolecular Chemistry·Mandapati Bhargava ReddyRamasamy Anandhan
Sep 19, 2017·Journal of the American Chemical Society·Richard C WalrothKyle M Lancaster
Dec 16, 2021·Chemical Communications : Chem Comm·Shi-Jun LiDe-Cai Fang

❮ 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.

Related Papers

Dalton Transactions : an International Journal of Inorganic Chemistry
Paweł J FigielArmando J L Pombeiro
Dalton Transactions : an International Journal of Inorganic Chemistry
Zhengliang LuJan Reedijk
© 2022 Meta ULC. All rights reserved