Heteroditopic NHC Ligand Supported Manganese(I) Complexes: Synthesis, Characterization, and Activity as Non-bifunctional Phosphine-Free Catalyst for the α-Alkylation of Nitriles.

In the present work, several manganese(I) complexes of chelating heteroditopic ligands Mn1-3, featuring ImNHC (imidazol-2-ylidene) connected to a 1,2,3-triazole-N or tzNHC (1,2,3-triazol-5-ylidene) donors via a methylene spacer, with possible modifications at the triazole backbone have been synthesized and completely characterized. Notably, the CO stretching frequencies, electrochemical analysis, and frontier orbital analysis certainly suggest that the chelating ImNHC-tzNHC ligands have stronger donation capabilities than the related ImNHC-Ntz ligand in the synthesized complexes. Moreover, these well-defined phosphine-free Mn(I)-NHC complexes have been found to be effective non-bifunctional catalysts for the α-alkylation of nitriles using alcohols and importantly, the catalyst Mn1 containing ImNHC connected to a weaker triazole-N donor displayed higher activity compared to Mn2/Mn3 containing an unsymmetrical bis-carbene donors (ImNHC and tzNHC).

N-Heterocyclic Carbene-Supported Nickel-Catalyzed Selective (Un)Symmetrical N-Alkylation of Aromatic Diamines with Alcohols.

The "borrowing hydrogen" (BH) approach for the N-alkylation of phenylenediamines using alcohols as coupling partners is highly challenging due to the selectivity issue of the generated products. Furthermore, the development of base-metal systems that can potentially substitute precious metals with competitive activity is a major challenge in BH catalysis. We present herein an efficient protocol for the N,N'-di-alkylation of aromatic diamines using an in situ-generated Ni-NHC complex from NiCl and the ligand , which gave access to a wide range of N,N'-di-alkylated orthophenylene diamines (rather than the generally observed benzimidazole derivatives), - and -phenylene diamines along with 2,6-diamino pyridine derivatives in good to excellent yields.

Ru-Complexes of heteroditopic chelating NHC ligands: effective catalysts for the β-alkylation of secondary alcohols and the synthesis of 2-alkylaminoquinoline derivatives following the dehydrogenative protocol.

Ru-Complexes of chelating heteroditopic N-heterocyclic carbene ligands featuring imidazol-2-ylidene (ImNHC) and 1,2,3-triazol-5-ylidene (tzNHC) donors connected a CH spacer, 1a-c, were found to be very effective catalysts for the cross-coupling of secondary and primary alcohols with the elimination of HO. Diverse β-alkylated secondary alcohols were thus obtained by following this method in excellent yields of up to 95% by employing a very low catalyst (1a) loading of 0.01-0.

Recent Advances in the Syntheses and Catalytic Applications of Homonuclear Ru-, Rh-, and Ir-Complexes of C ^C Cyclometalated Ligands.

In the past few decades, chemistry of cyclometalated species has gained momentum with increased applications in several areas of scientific developments. Cyclometalation reactions result in the formation of stable metallacycles through the generation of metal-carbon covalent bonds by activating the unreactive Csp -H or Csp -H bonds. The extra stability gained by the formation of metallacycles enhances their applicability scopes especially in the area of homogeneous catalysis.

[(PPh)NiCl]-Catalyzed C-N Bond Formation Reaction via Borrowing Hydrogen Strategy: Access to Diverse Secondary Amines and Quinolines.

Commercially available [(PPh)NiCl] was found to be an efficient catalyst for the mono--alkylation of (hetero)aromatic amines, employing alcohols to deliver diverse secondary amines, including the drug intermediates chloropyramine () and mepyramine (), in excellent yields (up to 97%) via the borrowing hydrogen strategy. This method shows a superior activity (TON up to 10000) with a broad substrate scope at a low catalyst loading of 1 mol % and a short reaction time. Further, this strategy is also successful in accessing various quinoline derivatives following the acceptorless dehydrogenation pathway.

Transition metal complexes of a bis(carbene) ligand featuring 1,2,4-triazolin-5-ylidene donors: structural diversity and catalytic applications.

Dialkylation of the 1,3-bis(1,2,4-triazol-1-yl)benzene with ethyl bromide results in the formation of [L-H2]Br2 which, upon salt metathesis with NH4PF6, readily yields the bis(triazolium) salt [L-H2](PF6)2 with non-coordinating counterions. [L-H2](PF6)2 and Ag2O react in a 1 : 1 ratio to yield a binuclear AgI-tetracarbene complex of the composition [(L)2Ag2](PF6)2 which undergoes a facile transmetalation reaction with [Cu(SMe2)Br] to deliver the corresponding CuI-NHC complex [(L)2Cu2](PF6)2. In contrast, the [L-H2]Br2 reacts with [Ir(Cp*)Cl2]2 to generate a doubly C-H activated IrIII-NHC complex 5.

Ruthenium(II) Complexes of Heteroditopic N-Heterocyclic Carbene Ligands: Efficient Catalysts for C-N Bond Formation via a Hydrogen-Borrowing Strategy under Solvent-Free Conditions.

Both imidazol-2-ylidene (ImNHC) and 1,2,3-triazol-5-ylidene (tzNHC) have evolved to be elite groups of N-heterocyclic carbene (NHC) ligands for homogeneous catalysis. To develop efficient ruthenium(II)-based catalysts incorporating these ligands for C-N bond-forming reactions via hydrogen-borrowing methodology, we utilized chelating ligands integrated with ImNHC and mesoionic tzNHC donors connected via a CH spacer with a diverse triazole backbone. The synthesized ruthenium(II) complexes are found to be highly efficient for C-N bond formation across a wide range of primary amine and alcohol substrates under solvent-free conditions, and among all of the complexes studied here, catalyst with a mesityl substituent displayed maximum activity.

Catalyst-Free and Solvent-Free Facile Hydroboration of Imines.

A facile process for the catalyst-free and solvent-free hydroboration of aromatic as well as heteroaromatic imines is reported. This atom-economic methodology is scalable, compatible with sterically and electronically diverse imines, displaying excellent tolerance towards various functional groups, and works efficiently at ambient temperature in most of the cases, affording secondary amines in good to excellent yield after hydrolysis.

Effect of Ancillary Ligand in Cyclometalated Ru(II)-NHC-Catalyzed Transfer Hydrogenation of Unsaturated Compounds.

In an effort to develop efficient Ru(II)-NHC-based catalyst considering their stereoelectronic effect for hydride-transfer reaction, we found that the ancillary NHC ligand can play a significant role in its catalytic performance. This effect is demonstrated by comparing the activity of two different types of orthometalated precatalysts of general formula [( p-cymene)(NHC)Ru(X)] (NHC = an imidazolylidene-based ImNHC, compound 2a-c, or a mesoionic triazolylidene-based tzNHC, compound 4) in transfer hydrogenation of carbonyl substrates. The electron-rich precatalyst, 2c, containing p-OMe-substituted NHC ligand performed significantly better than both unsubstituted complex 2a and p-CF substituted electron-poor complex 2b in ketone reduction.

Purification and characterization of an antifungal chitinase from Citrobacter freundii str. nov. haritD11.

The purpose of the research was to study the purification and partial characterization of antifungal alkaline chitinase from a newly isolated Citrobacter freundii haritD11. The enzyme was purified in a three-step procedure involving ammonium sulfate precipitation, dialysis, and Sephadex G-100 gel filtration chromatography. The enzyme was shown to have a relative high molecular weight of 64 kDa by sodium dodecyl sulfate polyacrylamide gel electrophoresis and was purified 7.

Novel Pyridinium compound from marine actinomycete, Amycolatopsis alba var. nov. DVR D4 showing antimicrobial and cytotoxic activities in vitro.

Marine sediment samples from Visakhapatnam coast of Bay of Bengal, India, were investigated as a source of actinomycetes to screen for the production of antibiotics and cytotoxic compounds. Actinomycete strain DVR D4 with interesting bioactivity profile was isolated during our systematic study of marine actinomycetes. Based on biochemical properties and 16S rDNA analysis the isolate DVR D4 was identified as a strain of Amycolatopsis alba.