Resonance Raman and FTIR spectra of isotope-labeled reduced 1,4-benzoquinone and its protonated forms in solutions
Resonance Raman (RR) and FTIR spectra are observed for 1,4-benzoquinone and its 18O2 and d4 isotopomers in their reduced states and their protonated forms, including the anion radical, semiquinone radical, dianion, and pro
Development of isotope-enriched phosphatidylinositol-4- And 5-phosphate cellular mass spectrometry probes
Synthetic phosphatidylinositol phosphate (PtdInsPn) derivatives play a pivotal role in broadening our understanding of PtdInsPnmetabolism. However, the development of such tools is reliant on efficient enantioselective and regioselective synthetic strategies. Here we report the development of a divergent synthetic route applicable to the synthesis of deuterated PtdIns4Pand PtdIns5Pderivatives. The synthetic strategy developed involves a key enzymatic desymmetrisation step using Lipozyme TL-IM. In addition, we optimised the large-scale synthesis of deuteratedmyo-inositol, allowing for the preparation of a series of saturated and unsaturated deuterated PtdIns4Pand PtdIns5Pderivatives. Experiments in MCF7 cells demonstrated that these deuterated probes enable quantification of the corresponding endogenous phospholipids in a cellular setting. Overall, these deuterated probes will be powerful tools to help improve our understanding of the role played by PtdInsPnin physiology and disease.
Joffrin, Amélie M.,Saunders, Alex M.,Barneda, David,Flemington, Vikki,Thompson, Amber L.,Sanganee, Hitesh J.,Conway, Stuart J.
p. 2549 - 2557
(2021/03/01)
Effects of B2pin2 and PCy3 on copper-catalyzed trifluoromethylation of substituted alkenes and alkynes with the Togni reagent
The copper-catalyzed oxytrifluoromethylation of phenylacetylenes and C-H trifluoromethylation of quinones were studied. It was found that both reactions are accelerated by B2pin2 and PCy3 additives. The two reactions have different substituent effects. The oxytrifluoromethylation is faster in the presence of electron-donating groups, while the C-H trifluoromethylation is faster with electron-withdrawing substituents. The Hammett plot for oxytrifluoromethylation gave a ρ value of -0.76 indicating electron demand in the rate determining step of the reaction. According to the absolute value of ρ the reaction probably does not proceed through a rate determining formation of a carbocation intermediate. The kinetic isotope effect measurements indicate that in C-H trifluoromethylation of quinones the cleavage of the C-H bond is not the rate determining step of the reaction.
Janson, P?r G.,Ilchenko, Nadia O.,Diez-Varga, Alberto,Szabó, Kálmán J.
p. 922 - 931
(2015/03/30)
Reductive Dehalogenation and Ring Saturation of Halogenated Hydroquinones, Catechol, and Resorcinol with Raney Alloys in NaOD-D2O Solution Leading to Hydroquinones, 1,4-Cyclohexanediol and 1,3-Cyclohexanedione Labeled with Deuterium