Refernces
10.1021/ic502791y
The solid-phase synthesis and screening platform was successful in identifying lead caging groups that release ligands with visible light, demonstrating the utility of this approach for discovering new metal-based caging groups.
10.1002/anie.200461462
The research focuses on the synthesis and characterization of unprecedented dicopper(II) complexes featuring a bridging phenoxyl radical, which exhibit an S = 3/2 spin state. The experiments involved mixing two equivalents of Cu(ClO4)2·6H2O with the dinucleating ligand HL in acetonitrile, in the presence of NEt3, to obtain the complex [L(CH3CN)2Cu2]3+ (1). Further reactions with different copper salts and varying conditions led to the formation of complexes [L(mOH)Cu2]2+ (2) and [L’Cu]2 2+ (3). The crystal structures of these complexes were determined using X-ray crystallography, and their electronic properties were analyzed through UV/Vis spectroscopy and EPR spectroscopy. Cyclic voltammetry was also employed to study their redox behavior. The research revealed that the structure of the complex has a minor effect on the oxidation potential of the m-phenolato ligand, and that the one-electron-oxidized forms of the complexes exhibit phenoxyl radical characteristics. The findings suggest that these m-phenoxyl dicopper(II) complexes, with their ferromagnetically exchange-coupled spins, could have biological relevance and potential applications in the study of new chemical properties.
10.1002/adsc.200700333
The research focuses on the copper-catalyzed multicomponent reactions (MCRs) of terminal alkynes, acid chlorides, and carbodiimides to synthesize functionalized propiolamidine derivatives. The study explores the efficiency of various bases and solvents to optimize the reaction conditions. The optimal catalytic system was found to be a combination of CuI, triethylamine (TEA), and acetonitrile (CH3CN), yielding the desired products in good to excellent yields. The experiments involved a suspension of carbodiimide and acid chloride, followed by the addition of anhydrous acetonitrile, TEA, CuI, and alkyne at room temperature under a nitrogen atmosphere. The reaction mixture was stirred, then extracted with CH2Cl2, washed with saturated NaHCO3 solution and water, dried over anhydrous MgSO4, and evaporated under vacuum. The residue was purified using silica gel column chromatography with petroleum ether/ethyl acetate as the eluent. The analysis of the reaction products was based on isolated yields, which were calculated based on the amount of N,N’-dialkylcarbodiimides used.
10.1080/00397910802419680
The research focuses on the efficient synthesis of 7-amino-3-hydroxyindan-1-one, a three-dimensional, three-point scaffold with potential applications in constructing focused compound libraries for biological interactions. The synthesis is achieved through a three-step process: first, reacting 4-nitrophthalic anhydride with ethyl acetoacetate, acetic anhydride, and triethylamine in methylene chloride to produce compound 10; second, hydrolyzing and decarboxylating compound 10 with trifluoroacetic acid in acetonitrile to yield 4-nitroindan-1,3-dione (11); and third, reducing compound 11 using catalytic hydrogenation with 10% Pd/C in methanol to obtain the final product, 7-amino-3-hydroxyindan-1-one (7). The structure of compound 7 was confirmed using heteronuclear multiple bond correlation (HMBC) spectral studies. The article also details the preparation of N-substituted derivatives of compound 7 and provides their physical constants, spectral data, and yields. Analytical techniques used include NMR spectroscopy, LC/MS, and melting point determination, ensuring the purity and structure of the synthesized compounds.
10.1016/j.ica.2014.06.004
The research focuses on the synthesis, structural characterization, and oxidative electrochemistry of various mono- and bisphosphine sulfides and selenides. The study involves the preparation of these compounds by reacting phosphines with sulfur or selenium, followed by characterization using NMR spectroscopy and X-ray crystallography. Eleven compounds were analyzed through X-ray crystal structures, and the percent buried volume was determined to estimate steric bulk. The oxidation of these chalcogenides was examined using cyclic voltammetry in methylene chloride and acetonitrile, with the solvent's effect on the oxidation potentials being minimal. The study observed that mono- and bisphosphine chalcogenides displayed an irreversible oxidative wave, with many phosphine selenides also showing a reductive wave indicative of Se–Se bond formation upon oxidation. However, the oxidation products could not be isolated. The research provides insights into the electronic properties and reactivity of phosphine sulfides and selenides, contributing to the understanding of their behavior in oxidative conditions.
10.1016/j.tetlet.2009.03.023
The research focuses on the synthesis of 3-alkylidene-piperidin-4-ones, which are structurally significant compounds found in many biologically active molecules with potential antibacterial and antitumor properties. The study presents a one-pot cascade transylidation-olefination sequence for the synthesis of these compounds with diverse C-5 substitution patterns. The process involves the use of tributylphosphorus ylides, which exhibit higher reactivity compared to triphenyl analogs, and t-butanol as the preferred solvent for transylidation. The Wittig olefination step, crucial for the synthesis, is found to be more effective with aliphatic aldehydes in MeCN as the solvent. The research concludes that this method is effective for synthesizing 3-alkylidene-piperidin-4-ones, with the utility demonstrated by the synthesis of a compound that cannot be prepared by conventional ketone α-alkylation due to steric hindrance. The study also notes that the application of this protocol to the synthesis of bioactive natural products is ongoing.
10.1016/S0022-328X(99)00709-3
The study in the Journal of Organometallic Chemistry focuses on the direct nucleophilic displacement of halides (chlorine or iodine) in compounds with the formula (Me3Si)3CSiRRX, where R and R represent various organic groups. The researchers investigated the reactions of these compounds with nucleophiles such as KOCN, KSCN, KCN, or NaN3 in different solvents like CH3CN, MeOH, and DMSO, or CH3CN mixed with H2O. The study explores the influence of steric hindrance on the reactivity of silicon centers bearing the bulky trisyl group (Tsi). It was found that by reducing the steric hindrance or using linear nucleophiles, direct bimolecular displacement reactions occur without the observation of rearrangement. The study also successfully synthesized new compounds with different groups and examined their reactivity with the mentioned nucleophiles, providing insights into the ease of reactions on silicon centers bearing the bulky trisyl group.
10.1021/acs.organomet.7b00603
The study investigates the impact of ligands on the reactivity of iron complexes in the reductive radical cyclization of unsaturated organic halides. It focuses on the role of ligands in the structure and reactivity of active anionic iron(I) hydride and borohydride species. The researchers synthesized an iron(II) borohydride complex, [(η1-H3BH)FeCl(NCCH3)4], and compared its catalytic properties with those of the iron(II) hydride complex, [HFeCl(dppe)2]. The study found that the ligand environment significantly influences the catalyst's ability to activate substrates, with the borohydride complex being more effective in activating both iodo- and bromoacetals compared to the hydride complex. The research provides new insights into the design of radical mediators, emphasizing the importance of ligand tailoring on the metal center for successful catalysis.
10.1021/jacs.7b00147
The study presents a novel physical organic approach to designing persistent, cyclable, low-potential electrolytes for nonaqueous redox flow batteries (RFBs), which are crucial for grid-scale energy storage. The researchers address the challenge of developing electrolytes that can operate at low or high potentials with the necessary stability and cycling lifetimes. They report the identification of a new pyridinium-based anolyte that can undergo electrochemical charge-discharge cycling at a low potential of -1.21 V versus Fc/Fc+ with minimal capacity loss after 200 cycles. The study involves the use of physical organic tools to predict and target electrolytes with the desired properties, applying this approach to a test case of anolyte candidate 1+. Through a systematic workflow that includes synthesis, decomposition rate measurements, physical-organic parameter identification, mathematical modeling, and validation, the researchers demonstrate the development of anolytes with enhanced persistence and low redox potentials, showing the potential for improving the performance and lifespan of RFBs.
10.1021/op500386g
The study outlines an efficient and practical synthesis process for ramelteon, a sedative-hypnotic drug used for treating insomnia. The novel synthesis involves the use of acetonitrile as a nucleophilic reagent to add to 4,5-dibromo-1,2,6,7-tetrahydro-8H-indeno[5,4b]furan-8-one, followed by a catalytic hydrogenation step that合并了debromination, dehydration, olefin reduction, and cyano reduction into one operation, resulting in the ethylamine compound. The process utilizes dibenzoyl-L-tartaric acid for salt formation and as a resolution agent, leading to the target compound ramelteon with an overall yield nearly double that of existing methods. The study emphasizes the avoidance of the traditional Wittig-Horner reaction, simplifying the synthesis with cost-effective reagents and reduced reaction steps.
10.3762/bjoc.9.240
The research presents a mild, efficient, and ligand-free method for the direct arylation of 5-pyrazolones using Pd-catalyzed C–H bond activation. The study focuses on the synthesis of 4-aryl-5-pyrazolones, which are significant heterocyclic compounds used in medicinal and biological research. The experiments involved the reaction of 5-pyrazolones with aryl halides using Pd(OAc)2 as a catalyst, with optimization of reaction conditions including the use of different bases, catalysts, solvents, and reaction temperatures. The results were analyzed in terms of product yield, and the optimal conditions were identified as using 0.1 equiv Pd(OAc)2 catalyst, 2.0 equiv Ag2CO3, acetonitrile solvent, 90 °C, air atmosphere, a 1:2 molar ratio of 5-pyrazolone to aryl halide, and a reaction time of 12 hours. The scope of the reaction was also tested with various aryl halides and 5-pyrazolone substrates, showing moderate to excellent yields. The research was supported by several foundations and the characterization data for all compounds is provided in the supporting information.
10.1016/j.tetlet.2008.11.036
The research discusses the use of zinc selenolates for nucleophilic cleavage of lactones and esters, utilizing a method that involves the generation of zinc selenolate from diselenides in the presence of Zn/AlCl3. The study aimed to develop a mild and neutral synthetic procedure that avoids the use of hazardous solvents and strong bases. The main reactants in the experiments were diaryl diselenides, zinc dust, anhydrous aluminum chloride, and various lactones or esters. The reactions were conducted in dry acetonitrile at 70°C under aerial conditions. The products were characterized using techniques such as 1H and 13C NMR, IR spectroscopy, mass spectroscopy, and elemental analysis, yielding carboxylic acids with moderate to excellent yields. The research demonstrated that zinc selenolate is an effective reagent for SN2-type cleavage of lactones and esters under relatively mild conditions, offering advantages in terms of operational simplicity and cost over previously reported methods.
10.1039/c4ob02208d
The research focuses on the development of a mild and efficient method for the conversion of arylboronic acids into arylthiocyanates using a copper-catalyzed aerobic oxidative process. The study employs trimethylsilylisothiocyanate (TMSNCS) as a thiocyantion reagent and utilizes NaF as a promoter under an oxygen atmosphere, with CuCl serving as the catalyst. The cross-coupling reaction is conducted at ambient temperature and is found to be effective for a broad range of functional groups, including strong electron-withdrawing groups. The experiments involve the optimization of reaction conditions, including the evaluation of various catalysts, ligands, additives, and solvents, ultimately leading to the identification of an optimal condition that involves the use of 20 mol% CuCl, 20 mol% TMEDA as a ligand, 1 equiv. of NaF, and 4 equiv. of K2CO3 in acetonitrile at room temperature for 12 hours, with 3? molecular sieves. The substrate scope was also investigated, demonstrating the versatility of the method with both electron-donating and electron-withdrawing arylboronic acids. The reaction mechanism is proposed based on the formation and reactivity of CuSCN as an intermediate, with both TMEDA and O2 being essential for the transformation. The study concludes that the developed protocol offers a milder and more efficient approach for aromatic oxidative thiocyanation, with potential applications in the synthesis of a variety of aryl thiocyanates.
10.1021/ol202395s
The research focuses on the insertion of benzynes into the PdN bond of P-alkenyl(alkynyl)-λ5-phosphazenes, leading to the formation of 1,4-benzazaphosphorinium triflates through a series of reactions including retro [2+2] cycloaddition/6π electrocyclization/protonation. The experiments involved the reaction of benzynes, generated from 2-(trimethylsilyl)phenyl triflates, with various P-alkenyl-λ5-phosphazenes in the presence of CsF as a reagent, using acetonitrile as a solvent. The reactions were carried out under a nitrogen atmosphere at 25°C, and the products were analyzed using analytical and spectral data, with some structures confirmed through X-ray crystal structure determination. The study also explored the scope of the reaction with different N-arylP-vinyl-λ5-phosphazenes, as well as related P-alkynyl derivatives and phosphane sulfides, optimizing conditions to achieve high yields of the desired products.
F, 
Xn, 
Xi, 
T
F:Flammable;
