Single-Electron Oxidation-Initiated Enantioselective Hydrosulfonylation of Olefins Enabled by Photoenzymatic Catalysis.

Controlling the enantioselectivity of hydrogen atom transfer (HAT) reactions has been a long-standing synthetic challenge. While recent advances on photoenzymatic catalysis have demonstrated the great potential of non-natural photoenzymes, all of the transformations are initiated by single-electron reduction of the substrate, with only one notable exception. Herein, we report an oxidation-initiated photoenzymatic enantioselective hydrosulfonylation of olefins using a novel mutant of gluconobacter ene-reductase (GluER-W100F-W342F). Compared to known photoenzymatic systems, our approach does not rely on the formation of an electron donor-acceptor complex between the substrates and enzyme cofactor and simplifies the reaction system by obviating the addition of a cofactor regeneration mixture. More importantly, the GluER variant exhibits high reactivity and enantioselectivity and a broad substrate scope. Mechanistic studies support the proposed oxidation-initiated mechanism and reveal that a tyrosine-mediated HAT process is involved.

Cobalt-Catalyzed Cyclization of 2-Bromobenzamides with Carbodiimides: A New Route for the Synthesis of 3-(Imino)isoindolin-1-ones.

A novel synthetic pathway to approach 3-(imino)isoindolin-1-ones by the Co-catalyzed cyclization reaction of 2-bromobenzamides with carbodiimides has been developed. This catalytic reaction can tolerate a variety of substituents and provide corresponding products in moderate yields for most cases. According to the literature, the reaction mechanism is proposed through the formation of a five-membered aza-cobalacycle complex, which carries out the following reaction subsequence, including nucleophilic addition and substitution, to furnish the desired structures.

Synthesis, density functional theory (DFT) studies and urease inhibition activity of chiral benzimidazoles.

A variety of benzimidazole by the heterocyclization of orthophenylenediamine were synthesized in 69-86% yields. The synthesized compounds 3a-f and 6a-f were characterized and further investigated as jack bean urease inhibitors. Density functional theory (DFT) studies were performed utilizing the basis set B3LYP/6-31G (d, p) to acquire perception into their structural properties. Frontier molecular orbital (FMO) analysis of all compounds 3a-f and 6a-f was computed at the same level of theory to get a notion about their chemical reactivity and stability. The mapping of the molecular electrostatic potential (MEP) over the entire stabilized molecular geometry indicated the reactive centers. They exhibited urease inhibition activity with IC50 between 22 and 99 µM. Compounds containing withdrawing groups on the benzene ring (3d, 6d) were not showing significant urease inhibition. The value obtained for 3a, 3b, 3f had shown their significant urease inhibition for both theoretical and experimental. Notably, the compound having S-configuration (3a) (22.26 ± 6.2 µM) was good as compared to its R enantiomer 3f (31.42 ± 23.3 µM). Despite this, we elaborated the computational studies of the corresponding compounds, to highlight electronic effect which include HOMO, LUMO, Molecular electrostatic potential (MEP) and molecular docking.

(Diacetoxyiodo)benzene-Mediated C-H Oxidation of Benzylic Acetals.

A useful oxidation of C-H bond of benzylic acetals has been achieved. This method avoids the use of stoichiometric metals and is compatible with the presence of both electron-donating and electron-withdrawing substituents on the aromatic ring. Oxidation was carried out by rapid microwave irradiation of benzylic acetals with PhI(OAc)2 as the oxidant. This led to the oxidation of acetals into 2-acetoxy-1,3-dioxolanes. Furthermore, this transformation protocol encompasses a wide range of valuable conversions of these useful synthons into different carboxylic acid derivatives.