PMID: 11916414Mar 28, 2002Paper

Activation of acyl phosphate monoesters by lanthanide ions: enhanced reactivity of benzoyl methyl phosphate

Journal of the American Chemical Society
Ronald Kluger, Lisa L Cameron

Abstract

Acyl phosphate monoesters are intermediates in many biochemical acylation reactions, such as those involving aminoacyl adenylates. Benzoyl methyl phosphate, a typical acyl phosphate monoester, is slowly hydrolyzed in neutral solutions but reacts rapidly with amines. Since biochemical processes of acyl phosphate monoesters involve accelerated reactions with oxygen-centered nucleophiles, we sought catalysts for hydrolysis and methanolysis of benzoyl methyl phosphate to mimic the biochemical outcome. Lanthanide ions are particularly effective catalysts, accelerating reactions much more than comparable levels of magnesium ion. Detailed kinetic analysis of the hydrolysis reactions reveals formation of a 1:1 complex, followed by rapid reaction with a nucleophile. The hydroxide-dependent hydrolysis rate in the europium complex is about 10(5) times that of free substrate with hydroxide. A mechanism that accounts for the data and observed behavior involves bidentate coordination of the metal ion by the acyl phosphate through phosphate and carbonyl oxygens, lowering the energy of the tetrahedral addition intermediate and the associated transition states. The dependence of the metal ion catalyzed process on the concentration of hydroxide ...Continue Reading

Citations

Nov 2, 2005·Chemical Communications : Chem Comm·Nathan W Luedtke, Alanna Schepartz
Apr 20, 2010·Organic & Biomolecular Chemistry·Raj S Dhiman, Ronald Kluger
Jul 8, 2011·Organic & Biomolecular Chemistry·Raj S DhimanRonald Kluger
Jan 19, 2019·Nature Communications·Ahanjit BhattacharyaNeal K Devaraj
May 29, 2008·The Journal of Organic Chemistry·Jolanta Wodzinska, Ronald Kluger
Dec 7, 2007·Journal of the American Chemical Society·Svetlana Tzvetkova, Ronald Kluger
Nov 10, 2018·The Journal of Organic Chemistry·Jason M StevensMichael R Talley
Aug 26, 2004·Journal of the American Chemical Society·Lisa L CameronRonald Kluger
Nov 15, 2002·Journal of Medicinal Chemistry·Victoria NahumBilha Fischer

❮ Previous
Next ❯

Related Concepts

Related Feeds

Autoimmune Diseases

Autoimmune diseases occur as a result of an attack by the immune system on the body’s own tissues resulting in damage and dysfunction. There are different types of autoimmune diseases, in which there is a complex and unknown interaction between genetics and the environment. Discover the latest research on autoimmune diseases here.