Electrochemical Oxidation Enables Regioselective and Scalable α-C(sp3)-H Acyloxylation of Sulfides.

A highly selective, environmentally friendly, and scalable electrochemical protocol for the construction of α-acyloxy sulfides, through the synergistic effect of self-assembly-induced C(sp3)-H/O-H cross-coupling, is reported. It features exceptionally broad substrate scope, high regioselectivity, gram-scale synthesis, construction of complex molecules, and applicability to a variety of nucleophiles. Moreover, the soft X-ray absorption technique and a series of control experiments have been utilized to demonstrate the pivotal role of the self-assembly of the substrates, which indeed is responsible for the excellent compatibility and precise control of high regioselectivity in our electrochemical protocol.

I2-Catalyzed Oxidative Amidation of Benzylamines and Benzyl Cyanides under Mild Conditions.

We report a novel and efficient method for the oxidation of benzylic carbons (amines and cyanides) into corresponding benzamides using a catalytic amount of I2 and TBHP as the green oxidant via the C-H bond cleavage of the benzylic carbon under mild reaction conditions. According to the literature survey, this is the first report for the oxidative amidation of benzylamines and decyanation of benzyl cyanides in one pot under metal-free conditions.

Visible-light-promoted selective C-H amination of heteroarenes with heteroaromatic amines under metal-free conditions.

The regioselective C-H amination of quinoline amides (C5) and imidazopyridines (C3) under transition-metal-free conditions at room temperature with a high degree of functional group tolerance is reported. The C-H amination promoted by visible light in the presence of a photocatalyst with a wide range of heteroamines makes the present protocol more sustainable.

Phenyliodonium Diacetate Mediated Oxidative Functionalization of Styrenes with Molecular Oxygen: Synthesis of α-Oxygenated Ketones.

Synthesis of α-oxygenated ketones from styrenes mediated by phenyliodonium diacetate in the presence of molecular oxygen and N-hydroxyphthalimide or N-hydroxybenzotriazole has been described. Addition of carbonyl oxygen at the α-position and formation of C-O bond at the ß-position of styrenes was achieved under metal-free conditions. The present method is applicable for wide range of styrenes with a variety of functional groups.

Copper-Catalyzed Three-Component System for Arylsulfenylation of Imidazopyridines with Elemental Sulfur.

A one-pot three-component reaction for the regioselective synthesis of thioarylated imidazoheterocycles from aryl halides and elemental sulfur using copper(I) iodide as a catalyst has been developed. Reactions proceed with high efficiency and afford thioarylated imidazoheterocycles in good yields with broad functional group tolerance.

Copper-catalyzed C(sp(3))-H functionalization of ketones with vinyl azides: synthesis of substituted-1H-pyrroles.

Copper-catalyzed C(sp(3))-H functionalization of ketones with vinyl azides for the synthesis of substituted pyrroles has been developed. The method is a straightforward and efficient way to access a series of 2,3,5-trisubstituted-1H-pyrroles in modest to excellent yields with broad functional group tolerance under mild conditions.

Enantiopure 1,4,5-trisubstituted 1,2,3-triazoles from carbohydrates: applications of organoselenium chemistry.

A wide range of stable vinyl selenone-modified furanosides has been synthesized for the first time. These 2π-partners undergo 1,3-dipolar cycloaddition reactions with a wide range of organic azides to afford enantiopure trisubstituted triazoles. Furanosyl rings opened up during triazole synthesis to generate polyfunctionalized molecules, ready to undergo further transformations. This strategy is one of the most convenient methods for the synthesis of enantiopure 1,4,5-trisubstituted 1,2,3-triazoles where the chiral components are attached to C-4 or C-5 position of triazole ring. These triazoles are formed in a regioselective manner, and several pairs of regioisomeric triazoles have also been synthesized. The approach affords densely functionalized triazoles, which are amenable to further modifications because of the presence of aldehyde and hydroxyl groups. This powerful and practical route adds to the arsenals of chemists and biologists interested in the synthesis and applications of triazoles.

Transition metal-free oxidative esterification of benzylic alcohols in aqueous medium.

Oxidative esterification of benzylic alcohols with a catalytic amount of HBr-H2O2 in aqueous medium under mild conditions is reported with a wide range of substrate scope for both benzylic and aliphatic alcohols. The conditions are also suitable for selective mono-esterification of ethylene glycol and glycerol. With catalytic amounts of HBr (20 mol%) and H2O2, the generation of reactive intermediate species BrOH has been ascertained by UV-visible spectra.

Solar photothermochemical reaction and supercritical CO2 work up for a fully green process of preparation of pure p-nitrobenzyl bromide.

It has been reported by us recently that p-nitrobenzyl bromide (PNBBr) can be synthesized from p-nitrotoluene (PNT) in high isolated yield with respect to available bromine in 2:1 Br(-)-BrO3(-) employed as brominating reagent. The reaction was conducted in ethylene dichloride (EDC) and the substrate was taken in excess to suppress dibromo impurity formation. The product was "cold crystallized" from the reaction mass and the mother liquor was recycled in the subsequent batch thereby eliminating organic discharge. The present work attempts to further advance the synthesis of this commercially important molecule employed in protection-deprotection strategies. Herein its successful synthesis employing neat substrate and solar radiation as the sole energy source to drive this photothermochemical reaction is reported. Further, 100% pure PNBBr could be isolated from the solid reaction mass in 87% yield by leaching out the excess substrate through supercritical CO2 (Sc-CO2) extraction. The reaction was therefore accomplished cleanly in all respects and with low carbon footprint.

Electrochemical oxidation-induced etherification via C(sp3)─H/O─H cross-coupling.

Direct electrochemical construction of C─O bonds through C(sp3)─H functionalization still remains fundamentally challenging. Here, electrochemical oxidation-induced benzylic and allylic C(sp3)─H etherification has been developed. This protocol not only offers a practical strategy for the construction of C─O bonds using nonsolvent amounts of alcohols but also allows direct electrochemical benzylic and allylic C(sp3)─H functionalization in the absence of transition metal catalysis. A series of alcohols and benzylic and allylic C(sp3)─H compounds were compatible with this transformation. Mechanistically, the generation of aryl radical cation intermediates is the key to this C(sp3)─H etherification, as evidenced by radical probe substrate (cyclopropane ring opening) and electron paramagnetic resonance experiments.