13 research outputs found
PREPARATION OF 2-[4-(METHYLSULPHONYL)PHENYL]-2,3-DIHYDRO-OXAZOLO[2,3-A]ISOINDOL-5(9BH)- ONE DERIVATIVES AND A NEW SYNTHESIS OF THIAMPHENICOL ANALOGS
2-OXAZOLIDINONES AS REGIOSELECTIVE PROTECTION OF BETA-AMINO ALCOHOLS IN THE SYNTHESIS OF 2-AMINO-1-ARYL-3-FLUORO-1-PROPANOLS
Modulation of neurally mediated airway microvascular leakage in guinea-pig airways byβ 2 agonists
Design, Synthesis, and Herbicidal Activities of Novel 2-Cyanoacrylates Containing Isoxazole Moieties
Synthesis of 3-Aminoisoxazoles via the Addition−Elimination of Amines on 3-Bromoisoxazolines
Recyclization of 2-imino-2H-1-benzopyrans under the action of nucleophilic reagents: the novel approach for 2-(coumarin-3-yl)-3H-quinazolin-4-thiones
Carbon-sulfur bond-forming reaction catalysed by the radical SAM enzyme HydE.
International audienceCarbon-sulfur bond formation at aliphatic positions is a challenging reaction that is performed efficiently by radical S-adenosyl-L-methionine (SAM) enzymes. Here we report that 1,3-thiazolidines can act as ligands and substrates for the radical SAM enzyme HydE, which is involved in the assembly of the active site of [FeFe]-hydrogenase. Using X-ray crystallography, in vitro assays and NMR spectroscopy we identified a radical-based reaction mechanism that is best described as the formation of a C-centred radical that concomitantly attacks the sulfur atom of a thioether. To the best of our knowledge, this is the first example of a radical SAM enzyme that reacts directly on a sulfur atom instead of abstracting a hydrogen atom. Using theoretical calculations based on our high-resolution structures we followed the evolution of the electronic structure from SAM through to the formation of S-adenosyl-L-cysteine. Our results suggest that, at least in this case, the widely proposed and highly reactive 5'-deoxyadenosyl radical species that triggers the reaction in radical SAM enzymes is not an isolable intermediate