10.1016/j.tetlet.2014.02.046
The study presents an innovative method for the 1,4-addition of arylboronic acids to α,β-unsaturated substrates using nickel(I) complexes as catalysts. The nickel(I) species were generated in situ from Ni(PPh3)2Cl2 with the aid of activated iron, and the catalytic system was combined with NN'-bis(4-fluorobenzylidene) ethane-1,2-diamine (BFBED). The reaction is completed without the need for a base, but the presence of potassium iodide is essential. The study suggests a possible Ni(I)–Ni(III) catalytic cycle mechanism and demonstrates the efficiency of the method with yields up to 76%. The scope of the reaction was explored with various substrates and arylboronic acids, showing no significant influence from electron-withdrawing or electron-donating groups. The work provides a valuable contribution to the field of cross-coupling reactions, offering a more environmentally benign and cost-effective alternative to traditional noble metal catalysts.
10.1080/00958972.2010.534140
The research focuses on the synthesis, characterization, and evaluation of the antitumor and cytotoxic activities of a series of mononuclear Ru(II) complexes, specifically [Ru(T)2(S)]2t, where T represents 2,2'-bipyridine or 1,10-phenanthroline, and S denotes various thiosemicarbazone derivatives such as CH3-bitsz, Cl-bitsz, Br-bitsz, tmtsz, and dmtsz. The reactants used in the synthesis include hydrated ruthenium trichloride, 2,2'-bipyridine, 1,10-phenanthroline, and the thiosemicarbazone ligands. The complexes were characterized using UV-Vis, IR, 1H-NMR, FAB-mass spectroscopy, and elemental analysis. The antitumor activity was assessed in vivo against a transplantable murine tumor cell line (Ehrlich’s ascitic carcinoma), and the cytotoxic activity was evaluated in vitro against human cancer cell lines (Molt 4/C8 and CEM) and a murine tumor cell line (L1210). The study aimed to develop potential cytotoxins and explore the antitumor properties of these Ru(II) complexes as alternatives to platinum-based drugs, which are known for their high toxicity.
10.1021/acs.orglett.1c00626
The research focuses on the development of a stereo- and regioselective cis-hydrophosphorylation reaction of 1,3-enynes using visible-light irradiation of NiCl2(PPh3)2 as a catalyst. This reaction provides access to a variety of 1,3-dienes with good isolated yields. The experiments involved the use of NiCl2(PPh3)2, 1,10-phenanthroline as a ligand, Cs2CO3 as a base, and MeOH as a solvent. The reaction conditions were optimized to achieve the best yield of the desired (E)-1,3-diene products. Various 1,3-enynes and phosphine oxides were tested to establish the scope of the reaction. Analytical techniques such as NMR spectroscopy and X-ray crystallography were employed to determine the product yields, configurations, and structures. Preliminary mechanistic studies, including deuteration experiments and radical initiator tests, suggested a radical reaction pathway involving the generation of nickel phosphine species and their addition to the C≡C bond of the 1,3-enynes, followed by protonation to yield the cis-hydrophosphorylation products.
10.1039/c2dt32727a
This research details the synthesis and characterization of a series of metal-organic frameworks (MOFs) based on the 2-(m-methoxyphenyl)imidazole dicarboxylate ligand, m-H3MOPhIDC. The purpose of the study was to explore the coordination features of the imidazole dicarboxylate ligand and its influence on the assembly of MOFs with potential applications in gas storage, catalysis, and more. The researchers successfully synthesized seven coordination polymers with diverse structures ranging from one-dimensional chains to three-dimensional frameworks by controlling synthetic conditions such as solvent and pH values. The chemicals used in the process included the ligand m-H3MOPhIDC, various metal salts (Sr(NO3)2, Cd(NO3)2·4H2O, Cu(ClO4)2, and CoCl2·6H2O), auxiliary ligands (1,10-phenanthroline and 2,2'-bipyridine), and Et3N as a base. The conclusions highlighted the significant impact of reaction conditions, core metal ions, and auxiliary ligands on the structures of the resulting MOFs, and confirmed the versatility of the m-H3MOPhIDC ligand in constructing novel MOFs with interesting structures and properties.
10.1021/ol303164h
The study presents a mild method for synthesizing aryl and heteroaryl iodides through sequential C—H borylation and iodination. The key chemicals involved are aryl pinacol boronic esters, which are iodinated using CuI as the catalyst, phenanthroline as a ligand, and KI as the iodide source. The C—H borylation step is catalyzed by iridium, and the resulting boronic esters are then iodinated. This method leverages steric effects for regioselectivity, differing from traditional electronic or directing group effects. The process tolerates a wide range of functional groups, including tertiary amines, esters, amides, and nitriles, and can be applied to various arenes and heteroarenes. The study highlights the potential for synthesizing radiolabeled aryl iodides, demonstrated through the concise synthesis of a potential SPECT imaging agent.
10.1021/ol049827e
The study presents a copper sulfate-pentahydrate (CuSO?·5H?O) and 1,10-phenanthroline catalyzed cross-coupling protocol for synthesizing ynamides from alkynyl bromides and amides. This method is more environmentally friendly than using CuCN or copper halides and allows for the synthesis of various ynamides, including sulfonyl and heteroaromatic amine substituted ones. The researchers optimized the protocol by screening different Cu(I) and Cu(II) salts, ligands, solvents, concentrations, bases, and temperatures. They found that CuSO?·5H?O with 1,10-phenanthroline as the ligand provided the best results, yielding ynamides in good isolated yields and suppressing homocouplings. The protocol was successfully applied to a range of substrates, including previously poor ones like azacamphor, imidazolidinone, and acyclic urethanes, as well as lactams. It was also effective in preparing sulfonyl ynamides and vinylogous ynamides with various heteroaromatic amines, demonstrating its versatility and potential impact on organic synthesis.
10.1016/j.jorganchem.2004.04.030
The study explores the use of a modified conventional microwave oven for the synthesis of over 20 group 6 organometallic compounds, primarily focusing on molybdenum (Mo), tungsten (W), and chromium (Cr) carbonyls. The chemicals involved include hexacarbonyls such as Mo(CO)6, W(CO)6, and Cr(CO)6, which act as starting materials. These compounds react with various ligands, including mono-, bi-, and tridentate ligands like piperidine, 2,2'-bipyridine, 1,10-phenanthroline, pyridine, and phosphines (PPh3, dppm, dppe), to form tetracarbonyl and other complexes. The microwave-assisted reactions generally proceed without the need for an inert atmosphere, resulting in high yields and significantly reduced reaction times compared to conventional methods. For example, cis-[Mo(CO)4(dppe)] is prepared in >95% yield in just 20 minutes. The study also highlights the successful synthesis of dimeric molybdenum(I) cyclopentadienyl complexes, [CpMo(CO)3]2, in 94% yield, and dimolybdenum tetraacetate in 48% yield under an inert atmosphere. The microwave approach allows for the rapid formation of unsaturated, air-sensitive molybdenum-molybdenum triply bonded complexes, enabling complex organometallic reactions to be carried out more efficiently and safely, making them more accessible for both research and teaching purposes.
10.1002/anie.200800825
The study presents a nickel-catalyzed reductive coupling reaction for the regioselective synthesis of γ-amino esters, γ-aminonitriles, γ-aminosulfones, and pyrrolidinones, which are derivatives of γ-aminobutyric acid (GABA) and exhibit various biological properties with industrial applications. The reaction involves the coupling of aldimines and activated alkenes using a nickel-1,10-phenanthroline complex as the catalyst. Key chemicals used include 4-fluorobenzaldimine, ethyl acrylate, [NiBr2(phen)], [NiBr2(bipy)], [NiCl2(bipy)], and [NiBr2(phen)] as catalysts, with phenanthroline (phen) and bipyridine (bipy) as ligands. Zn and H2O were used as the reducing agent and proton source, respectively. The study highlights the importance of the choice of ligand and metal in the success of the reaction, with bipyridine-type ligands, particularly phen, being essential. The synthesized products serve as valuable building blocks in the pharmaceutical and chemical industries due to their potential biological activities.
10.1021/jo00298a049
The research focuses on the synthesis and investigation of the reactivity of two phenanthroline-linked dihydronicotinamides, compounds 3 and 6, which serve as models for the NADH-alcohol dehydrogenase coenzyme-enzyme complex. The purpose of this study was to examine whether the metal ion in these models could mimic the function of catalytic zinc in alcohol dehydrogenase, specifically in binding the substrate near the dihydronicotinamide group, orienting the groups for hydride transfer, and activating the carbonyl group for reduction. The researchers concluded that the metal ion in these models, particularly when Zn2+ is present, could effectively mimic the catalytic function of zinc in the enzyme complex, with hydride transfer occurring within a ternary complex. Key chemicals used in the process include 1,4-dihydro-l-(l,l0-phenanthrolin-2-ylmethyl)-3-pyridinecarboxamide (3), 1,4-dihydro-N-(l,l0-phenanthrolin-2-ylmethyl)-l-(phenylmethyl)-3-pyridinecarboxamide (6), 2,4,6-trinitrobenzene sulfonate (TNBS), methylene blue (MB+), and 2-pyridinecarboxaldehyde (PyCHO), along with various metal ions (M2+ = Zn2+, Co2+, Ni2+, Mg2+, and Cd2+).
T,
N
