Reactions of the cumyloxyl and benzyloxyl radicals with strong hydrogen bond acceptors. Large enhancements in hydrogen abstraction reactivity determined by substrate/radical hydrogen bonding

The Journal of Organic Chemistry
Michela SalamoneMassimo Bietti

Abstract

A kinetic study on hydrogen abstraction from strong hydrogen bond acceptors such as DMSO, HMPA, and tributylphosphine oxide (TBPO) by the cumyloxyl (CumO(•)) and benzyloxyl (BnO(•)) radicals was carried out in acetonitrile. The reactions with CumO(•) were described in terms of a direct hydrogen abstraction mechanism, in line with the kinetic deuterium isotope effects, k(H)/k(D), of 2.0 and 3.1 measured for reaction of this radical with DMSO/DMSO-d(6) and HMPA/HMPA-d(18). Very large increases in reactivity were observed on going from CumO(•) to BnO(•), as evidenced by k(H)(BnO(•))/k(H)(CumO(•)) ratios of 86, 4.8 × 10(3), and 1.6 × 10(4) for the reactions with HMPA, TBPO, and DMSO, respectively. The k(H)/k(D) of 0.91 and 1.0 measured for the reactions of BnO(•) with DMSO/DMSO-d(6) and HMPA/HMPA-d(18), together with the k(H)(BnO(•))/k(H)(CumO(•)) ratios, were explained on the basis of the formation of a hydrogen-bonded prereaction complex between the benzyloxyl α-C-H and the oxygen atom of the substrates followed by hydrogen abstraction. This is supported by theoretical calculations that show the formation of relatively strong prereaction complexes. These observations confirm that in alkoxyl radical reactions specific hydrogen bon...Continue Reading

References

Jun 15, 1986·Physical Review. B, Condensed Matter·J P Perdew
Jul 18, 2001·Journal of the American Chemical Society·B N NukunaV E Anderson
Sep 23, 2003·Angewandte Chemie·Maikel WijtmansNed A Porter
Dec 11, 2003·Chemical Reviews·Roger Atkinson, Janet Arey
Jun 17, 2004·Journal of the American Chemical Society·Meghan FinnJames M Tanko
Sep 9, 2004·Chemical Reviews·Bernard MeunierSason Shaik
Jan 13, 2006·Proceedings of the National Academy of Sciences of the United States of America·L MatthewsM E J Woolhouse
Aug 10, 2006·Chemical Reviews·Perry A FreyGeorge H Reed
Sep 28, 2006·Proceedings of the National Academy of Sciences of the United States of America·Lee M HoffartCarsten Krebs
Dec 21, 2006·Journal of the American Chemical Society·Mathieu FrenetteJuan C Scaiano
Jan 27, 2007·Science·E Vöhringer-MartinezB Abel
Mar 21, 2007·Accounts of Chemical Research·Grzegorz Litwinienko, K U Ingold
Jun 20, 2007·Chemical Society Reviews·Kevin R Campos
Jun 22, 2007·Organic Letters·Apurba L KonerWerner M Nau
Jul 20, 2007·Chemistry : a European Journal·Riccardo AmoratiCaterina Viglianisi
Jan 23, 2008·Chemical Communications : Chem Comm·Sushma MandaKazunori Anzai
Nov 29, 2008·Organic & Biomolecular Chemistry·Gonzalo Cosa, J C Scaiano
Feb 20, 2009·Angewandte Chemie·Chryssostomos ChatgilialogluQuinto G Mulazzani
Apr 3, 2009·The Journal of Physical Chemistry. B·Misaela Francisco-Marquez, Annia Galano
Jul 28, 2009·Journal of the American Chemical Society·Zachary I Watts, Christopher J Easton
Sep 23, 2009·Chemical Reviews·Paul R Ortiz de Montellano
Sep 23, 2009·Organic Letters·Brad D RoseCheryl D Stevenson
Nov 27, 2009·The Journal of Physical Chemistry. B·Tomonori KawashimaShunichi Fukuzumi
Jan 16, 2010·The Journal of Organic Chemistry·Sangit KumarLuca Valgimigli
Feb 11, 2010·Chemical Reviews·Ahmet Gunay, Klaus H Theopold
Feb 12, 2010·Journal of the American Chemical Society·Susan MitrokaJames M Tanko
Mar 11, 2010·Proceedings of the National Academy of Sciences of the United States of America·Jeffrey J Warren, James M Mayer
Apr 2, 2010·The Journal of Physical Chemistry. a·Andreas A Zavitsas
Apr 8, 2010·The Journal of Physical Chemistry. a·Hoang Q DoanJoseph S Francisco
Jun 10, 2010·Accounts of Chemical Research·Sason ShaikYong Wang
Sep 25, 2010·Angewandte Chemie·Takahiko KojimaShunichi Fukuzumi
Oct 28, 2010·Accounts of Chemical Research·James M Mayer
Nov 5, 2010·Journal of the American Chemical Society·Steve Scheiner, Tapas Kar
Nov 26, 2010·Journal of the American Chemical Society·Kimberly A ChoquetteRobert A Flowers

❮ Previous
Next ❯

Citations

Jul 5, 2013·Physical Chemistry Chemical Physics : PCCP·Manuel E MedinaJuan Raúl Alvarez-Idaboy
May 7, 2019·Chemistry : a European Journal·Lakshmanan Sandhiya, Herbert Zipse
Oct 11, 2017·The Journal of Physical Chemistry. a·Marwa K Abdel LatifJames M Tanko
Oct 7, 2021·Chemical Reviews·Liang ChangZhiwei Zuo

❮ 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.