Cobalt-Catalyzed Chemodivergent Synthesis of Cyclic Amines and Lactams from Ketoacids and Anilines Using Hydrosilylation.

Here, commercially available Co2(CO)8 was utilized as an efficient catalyst for chemodivergent synthesis of pyrrolidines and pyrrolidones from levulinic acid and aromatic amines under slightly different hydrosilylation conditions. 1.5 and 3 equiv of phenylsilane selectively yielded pyrrolidone and pyrrolidine, respectively. Various ketoacids and amines were successfully tested. Plausible mechanism involves the condensation of levulinic acid and amine to form an imine, which cyclizes to 3-pyrrolidin-2-one followed by reduction to pyrrolidone. The final reduction of pyrrolidone gave pyrrolidine.

Copper(i)-catalyzed click chemistry in deep eutectic solvent for the syntheses of ß-d-glucopyranosyltriazoles.

In the last two decades, click chemistry has progressed as a powerful tool in joining two different molecular units to generate fascinating structures with a widespread application in various branch of sciences. copper(i)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction, also known as click chemistry, has been extensively utilized as a versatile strategy for the rapid and selective formation of 1,4-disubstituted 1,2,3-triazoles. The successful use of CuAAC reaction for the preparation of biologically active triazole-attached carbohydrate-containing molecular architectures is an emerging area of glycoscience. In this regard, a well-defined copper(i)-iodide complex (1) with a tridentate NNO ligand (L1) was synthesized and effectively utilized as an active catalyst. Instead of using potentially hazardous reaction media such as DCM or toluene, the use of deep eutectic solvent (DES), an emerging class of green solvent, is advantageous for the syntheses of triazole-glycohybrids. The present work shows, for the first time, the successful use of DES as a reaction medium to click various glycosides and terminal alkynes in the presence of sodium azide. Various 1,4-disubstituted 1,2,3-glucopyranosyltriazoles were synthesized and the pure products were isolated by using a very simple work-up process (filtration). The reaction media was recovered and recycled in five consecutive runs. The presented catalytic protocol generated very minimum waste as reflected by a low E-factor (2.21-3.12). Finally, the optimized reaction conditions were evaluated with the CHEM21 green metrics toolkit.

Cobalt catalyzed chemoselective reduction of nitroarenes: hydrosilylation under thermal and photochemical reaction conditions.

Commercially available Co2(CO)8 was used as an effective catalyst for the hydrosilylation of nitroarenes under both thermal and photochemical conditions. A wide variety of nitroarenes with various functionalities were selectively reduced to aromatic amines. Syntheses of drug molecules expand the potential utility of this protocol. Experimental evidence suggested a radical pathway.

Nickel-Catalyzed α-Alkylation of Arylacetonitriles with Challenging Secondary Alcohols.

Nickel(II) complex 1 was utilized as a sustainable catalyst for α-alkylation of arylacetonitriles with challenging secondary alcohols. Arylacetonitriles with a wide range of functional groups were tolerated, and various cyclic and acyclic secondary alcohols were utilized to yield a large number of α-alkylated products. The plausible mechanism involves the base-promoted activation of precatalyst 1 to an active catalyst 2 (dehydrochlorinated product) which activates the O-H and C-H bonds of the secondary alcohol in a dehydrogenative pathway.

Manganese-Catalyzed Chemoselective Hydrosilylation of Nitroarenes: Sustainable Route to Aromatic Amines.

Herein we report efficient catalytic hydrosilylations of nitroarenes to form the corresponding aromatic amines using a well-defined manganese(II)-NNO pincer complex with a low catalyst loading (1 mol %) under solvent-free conditions. This base-metal-catalyzed hydrosilylation is an easy and sustainable alternative to classical hydrogenation. A large variety of nitroarenes bearing various functionalities were selectively transformed into the corresponding aromatic amines in good yields. The potential utility of the present catalytic protocol was demonstrated by the preparation of commercial drug molecules.

Efficient α-Alkylation of Arylacetonitriles with Secondary Alcohols Catalyzed by a Phosphine-Free Air-Stable Iridium(III) Complex.

A well-defined and readily available air-stable dimeric iridium(III) complex catalyzed α-alkylation of arylacetonitriles using secondary alcohols with the liberation of water as the only byproduct is reported. The α-alkylations were efficiently performed at 120 °C under solvent-free conditions with very low (0.1-0.01 mol %) catalyst loading. Various secondary alcohols including cyclic and acyclic alcohols and a wide variety of arylacetonitriles bearing different functional groups were converted into the corresponding α-alkylated products in good yields. Mechanistic study revealed that the reaction proceeds via alcohol activation by metal-ligand cooperation with the formation of reactive iridium-hydride species.

Hydrosilylation of Esters Catalyzed by Bisphosphine Manganese(I) Complex: Selective Transformation of Esters to Alcohols.

Selective and efficient hydrosilylations of esters to alcohols by a well-defined manganese(I) complex with a commercially available bisphosphine ligand are described. These reactions are easy alternatives for stoichiometric hydride reduction or hydrogenation, and employing cheap, abundant, and nonprecious metal is attractive. The hydrosilylations were performed at 100 °C under solvent-free conditions with low catalyst loading. A large variety of aromatic, aliphatic, and cyclic esters bearing different functional groups were selectively converted into the corresponding alcohols in good yields.