Enhancing Phosphate Diester Cleavage by a Zinc Complex through Controlling Nucleophile Coordination

Chemistry : a European Journal
Emmanuel Y Tirel, Nicholas H Williams

Abstract

Metal-ion complexes are the most effective artificial catalysts capable of cleaving phosphate diesters under mild aqueous conditions. A central strategy for making these complexes highly reactive has been to use ligand-based alcohols that are coordinated to the ion, providing an ionised nucleophile under neutral conditions but at the expense of deactivating it. We have created a highly reactive Zn complex that is 350-fold more reactive than an alcohol analogue by preventing the nucleophile binding to the metal ion. This strategy successfully delivers the benefits of efficient nucleophile delivery without strongly deactivating the metal ion Lewis acidity nor the oxyanion nucleophilicity. Varying the leaving group reveals that the transition state of the reaction is much further advanced than the reaction with hydroxide.

References

Sep 20, 1965·Journal of the American Chemical Society·R Breslow, D Chipman
Sep 30, 2005·Journal of the American Chemical Society·Guoqiang FengNicholas H Williams
Jan 26, 2006·Journal of the American Chemical Society·Jesse G Zalatan, Daniel Herschlag
Mar 16, 2006·Proceedings of the National Academy of Sciences of the United States of America·Gottfried K SchroederRichard Wolfenden
Dec 18, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Changlin Liu, Li Wang
May 23, 2009·The Journal of Organic Chemistry·Elisa S OrthFaruk Nome
Jul 25, 2009·Journal of the American Chemical Society·Renato BonomiFabrizio Mancin
Jan 25, 2011·Organic & Biomolecular Chemistry·Harri Lönnberg
May 1, 2012·Chemical Communications : Chem Comm·Fabrizio MancinPaolo Tecilla
Jul 24, 2013·Chemical Communications : Chem Comm·Paola Gómez-TagleAnatoly K Yatsimirsky
Nov 28, 2013·The Journal of Organic Chemistry·Fernanda DuarteShina Caroline Lynn Kamerlin
Jun 13, 2014·Angewandte Chemie·Emmanuel Y TirelNicholas H Williams

❮ Previous
Next ❯

Citations

Aug 17, 2016·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Fabrizio MancinPaolo Scrimin
Dec 20, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Dieter KrachtusPetra Imhof
May 3, 2018·Beilstein Journal of Organic Chemistry·Satu MikkolaHarri Lönnberg
Jan 30, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·José Carlos Lugo-GonzálezAnatoly K Yatsimirsky
Jan 16, 2021·Chembiochem : a European Journal of Chemical Biology·Lange Yakubu SalehTuomas Lönnberg
Feb 9, 2017·Inorganic Chemistry·José Carlos Lugo-GonzálezAnatoly K Yatsimirsky

❮ 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.