85020-76-4Relevant academic research and scientific papers
Organocatalytic Deuteration Induced by the Dynamic Covalent Interaction of Imidazolium Cations with Ketones
Ananikov, Valentine P.,Galkin, Konstantin I.,Gordeev, Evgeniy G.
, p. 1368 - 1378 (2021/01/18)
In this article, we suggest a new organocatalytic approach based on the dynamic covalent interaction of imidazolium cations with ketones. A reaction of N-alkyl imidazolium salts with acetone-d6 in the presence of oxygenated bases generates a dynamic organocatalytic system with a mixture of protonated carbene/ketone adducts acting as H/D exchange catalysts. The developed methodology of the pH-dependent deuteration showed high selectivity of labeling and good chiral functional group tolerance. Here we report a unique methodology for efficient metal-free deuteration, which enables labeling of various types of α-acidic compounds without trace metal contamination. (Figure presented.).
Engineering the promiscuous racemase activity of an arylmalonate decarboxylase
Kourist, Robert,Miyauchi, Yusuke,Uemura, Daisuke,Miyamoto, Kenji
experimental part, p. 557 - 563 (2011/03/21)
Variant G74C of arylmalonate decarboxylase (AMDase) from Bordatella bronchoseptica has a unique racemising activity towards profens. By protein engineering, variant G74C/V43A with a 20-fold shift towards promiscuous racemisation was obtained, based on a reduced activity in the decarboxylation reaction and a two-fold increase in the racemisation activity. The mutant showed an extended substrate range, with a 30-fold increase in the reaction rate towards ketoprofen. Molecular dynamics simulations and the substrate profile of the racemase indicate that the steric and polar effects of the substrate structure play a more dominant role on catalysis than mere kinetic α-proton acidity. The observation that the conversion of β,γ-unsaturated carboxylic acids does not lead to a rearrangement to form their α,β isomers indicates a concerted rather than a stepwise mechanism. Interestingly, a substrate bearing a nitro group instead of the carboxylic acid group on the α-carbon atom was also converted by the racemase.
An efficient laboratory synthesis of α-deuteriated profens
Coumbarides, Gregory S.,Dingjan, Marco,Eames, Jason,Flinn, Anthony,Northen, Julian
, p. 903 - 914 (2008/02/09)
An efficient and practical laboratory synthesis of a series of 2-deuterio-2-arylpropionic acids (α-deuterioprofens) is described. The levels of deuterium incorporation are high and the products are synthetically useful. Copyright
