Metal-Free Nitrogen-Doped Mesoporous Carbons for the Mild and Selective Synthesis of Pyrroles from Nitroarenes via Cascade Reaction.

The cascade synthesis of pyrroles from nitroarenes is an attractive alternative strategy. However, metal catalysts and relatively high temperatures cover the existing reported catalytic systems for this strategy. The development of nonmetallic heterogeneous catalytic systems for the one-pot synthesis of pyrrole from nitroarenes under mild conditions is both worthwhile and challenging. Herein, we describe an exceptionally efficient method for the synthesis of N-substituted pyrroles by the reductive coupling of nitroarenes and diketones over heterogeneous metal-free catalysts under mild conditions. Nonmetallic NC-X catalysts with high activity were prepared from the pyrolysis of well-defined ligands via simple sacrificing hard template methods. Hydrazine hydrate, formic acid, and molecular hydrogen can all be used as reducing agents in the hydrogenation/Paal-Knorr reaction sequence to efficiently synthesize various N-substituted pyrroles, including drugs and bioactive molecules. The catalytic system was featured with good tolerance to sensitive functional groups and no side reactions such as dehalogenation and aromatics hydrogenation. Hammett correlation studies have shown that the electron-donating substituents are beneficial for the one-pot synthesis of N-substituted pyrroles. The results established that the outstanding performance of the catalyst is mainly attributed to the contribution of graphitic N in the catalyst as well as the promotion effect of the mesoporous structure on the reaction.

Copper/Nitroxyl-Catalyzed Synthesis of Pyrroles by Oxidative Coupling of Diols and Primary Amines at Room Temperature.

The Cu/ABNO-catalyzed aerobic oxidative coupling of diols and primary amines to access N-substituted pyrroles is highlighted (ABNO = 9-azabicyclo[3.3.1]nonane N-oxyl). The reaction proceeds at room temperature with an O2 balloon as the oxidant using commercially available materials as the substrates and catalysts. The catalyst system is characterized by a broad range of substrates and a good tolerance to sensitive functional groups. The gram-scale experiment proves this system's practicability.

Cobalt Nanoparticles-Catalyzed Widely Applicable Successive C-C Bond Cleavage in Alcohols to Access Esters.

Selective cleavage and functionalization of C-C bonds have important applications in organic synthesis and biomass utilization. However, functionalization of C-C bonds by controlled cleavage remains difficult and challenging because they are inert. Herein, we describe an unprecedented efficient protocol for the breaking of successive C-C bonds in alcohols to form esters with one or multiple carbon atoms less using heterogeneous cobalt nanoparticles as catalyst with dioxygen as the oxidant. A wide range of alcohols including inactive long-chain alkyl aryl alcohols undergo smoothly successive cleavage of adjacent -(C-C)n - bonds to afford the corresponding esters. The catalyst was used for seven times without any decrease in activity. Characterization and control experiments disclose that cobalt nanoparticles are responsible for the successive cleavage of C-C bonds to achieve excellent catalytic activity, while the presence of Co-Nx has just the opposite effect. Preliminary mechanistic studies reveal that a tandem sequence reaction is involved in this process.

Selectivity-tunable amine aerobic oxidation catalysed by metal-free N,O-doped carbons.

Herein, we present a series of N,O-doped mesoporous carbons obtained at different pyrolysis temperatures as the first metal-free catalysts which successfully switch between imine and nitrile products for amine oxidation. Systematic characterization studies and control experiments revealed that the C-O group on the surface could function as a catalytically active site for nitrile synthesis and the N-doping environment was essential.

Metal-free catalysis of nitrogen-doped nanocarbons for the ammoxidation of alcohols to nitriles.

Here meso-N/C-900 derived from polypyridyl ligand DAA has been developed as a metal-free catalyst, for the first time, exhibiting good performance in catalytic ammoxidation of alcohols to nitriles. Systematic characterization suggests that the accessible mesopores and the effective pyridinic/pyrrolic-N are responsible for the unprecedented performance.

Iron/ABNO-Catalyzed Aerobic Oxidation of Alcohols to Aldehydes and Ketones under Ambient Atmosphere.

We report a new Fe(NO3)3·9H2O/9-azabicyclo[3.3.1]nonan-N-oxyl catalyst system that enables efficient aerobic oxidation of a broad range of primary and secondary alcohols to the corresponding aldehydes and ketones at room temperature with ambient air as the oxidant. The catalyst system exhibits excellent activity and selectivity for primary aliphatic alcohol oxidation. This procedure can also be scaled up. Kinetic analysis demonstrates that C-H bond cleavage is the rate-determining step and that cationic species are involved in the reaction.

Mesoporous carbon derived from vitamin B12: a high-performance bifunctional catalyst for imine formation.

Mesoporous carbon derived from natural vitamin B12 is applied for the first time in organic synthesis and exhibits exceptionally high dual activity for imine formation via the cross-coupling of alcohols with amines and the self-coupling of primary amines using molecular oxygen or air as the terminal oxidant.

An Effective Method for the Construction of Esters Using Cs2CO3 as Oxygen Source.

An effective method for the construction of esters from acyl chloride and halohydrocarbon using Cs2CO3 as an oxygen source was achieved for the first time. The methodology has a wide scope of substrates and can be scaled up. The study of a preliminary reaction mechanism demonstrated that the O in the products comes from Cs2CO3 and this esterification proceeds through a free radical reaction. It was also found that CO2 can also be used in this esterification reaction as an oxygen source.

Highly efficient oxidation of alcohols catalyzed by a porphyrin-inspired manganese complex.

A novel strategy for catalytic oxidation of a variety of benzylic, allylic, propargylic, and aliphatic alcohols to the corresponding aldehydes or ketones by an in situ formed porphyrin-inspired manganese complex in excellent yields (up to 99%) has been successfully developed.

Synergistic H4NI-AcOH Catalyzed Oxidation of the Csp(3)-H Bonds of Benzylpyridines with Molecular Oxygen.

The oxidation of benzylpyridines forming benzoylpyridines was achieved based on a synergistic H4NI-AcOH catalyst and molecular oxygen in high yield under solvent-free conditions. This is the first nonmetallic catalytic system for this oxidation transformation using molecular oxygen as the oxidant. The catalytic system has a wide scope of substrates and excellent chemoselectivity, and this procedure can also be scaled up. The study of a preliminary reaction mechanism demonstrated that the oxidation of the Csp(3)-H bonds of benzylpyridines was promoted by the pyridinium salts formed by AcOH and benzylpyridines. The synergistic effect of H4NI-AcOH was also demonstrated by control experiments.

A porphyrin-inspired iron catalyst for asymmetric epoxidation of electron-deficient olefins.

An in situ formed porphyrin-inspired iron complex that catalyzes asymmetric epoxidation of di- and trisubstituted enones is described. The reaction provides highly enantioenriched α,ß-epoxyketones (up to 99% ee). The practical utility of the new catalyst system is demonstrated by the gram-scale synthesis of optically pure epoxide. Hammett analysis suggests that the transition state of the reaction is electron-demanding and the active oxidant is electrophilic.

Asymmetric epoxidation of olefins with hydrogen peroxide by an in situ-formed manganese complex.

Asymmetric epoxidation of a variety of cis, trans, terminal, and trisubstituted olefins in excellent yields (up to 94%) and enantioselectivities (>99% ee) by an in situ-formed manganese complex using H2O2 has been developed. A relationship between the hydrophobicity of the catalyst imposed by ligand and the catalytic activity has been observed. The influence of the amount and identity of the acid additive was examined, and improved enantioselectivities were achieved through the use of a catalytic amount of a carboxylic acid additive.

Asymmetric oxidation catalysis by a porphyrin-inspired manganese complex: highly enantioselective sulfoxidation with a wide substrate scope.

The first genuinely promising porphyrin-inspired manganese-catalyzed asymmetric sulfoxidation method using hydrogen peroxide has been successfully developed, allowing for rapidly oxidizing (0.5-1.0 h) a wide variety of sulfides in high yields with excellent enantioselectivities (up to >99% ee).

Asymmetric epoxidation of alkenes catalyzed by a porphyrin-inspired manganese complex.

A novel strategy for catalytic asymmetric epoxidation of a wide variety of olefins by a porphyrin-inspired chiral manganese complex using H2O2 as a terminal oxidant in excellent yield with up to greater than 99% ee has been successfully developed.

Selective oxidation of unsaturated alcohols catalyzed by sodium nitrite and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone with molecular oxygen under mild conditions.

We have developed a simple and practical process for the oxidation of alcohols to the corresponding carbonyl compounds by using a low catalytic amount of DDQ, NaNO(2) as a cocatalyst, and molecular oxygen as terminal oxidant. Nitric oxide generated in situ by NaNO(2) in the presence of AcOH is essential for the realization of the catalytic cycle at room temperature. The practical utility of this catalytic process has been demonstrated in the gram-scale oxidation of cinnamyl alcohol.