10.1021/ja1084749
The study conducted by Roland Appel, Nicolai Hartmann, and Herbert Mayr from the Department of Chemistry at Ludwig-Maximilians-Universit?t München, investigates the cyclopropanation reactions using sulfur ylides. It focuses on the rates of reactions between stabilized and semistabilized sulfur ylides with benzhydrylium ions and Michael acceptors, measured using UV-vis spectroscopy in DMSO at 20°C. The research establishes a correlation between the second-order rate constants (log k2) and the electrophilicity parameters (E) of the electrophiles, which aids in calculating the nucleophile-specific parameters (N and s) for the sulfur ylides. The findings indicate that the rate constants for cyclopropanation reactions with Michael acceptors align with those for carbocations, suggesting a stepwise mechanism with the initial nucleophilic attack being rate-determining. This study provides a quantitative approach to understanding sulfur ylide reactivity, which is crucial for predicting the scope and limitations of cyclopropanation reactions in organic synthesis.
10.1002/chem.201804416
The study, authored by Nicola Lucchetti and Ryan Gilmour, presents a novel approach to chemical glycosylation, which is a critical process in the synthesis of carbohydrates. It introduces a direct, metal-free method for the anomeric O-arylation of unactivated carbohydrates, bypassing the need for pre-functionalization of the substrate. This method employs stable aryliodonium salts to facilitate a formal O?H functionalization reaction at ambient temperature, leading to the formation of acetals directly from reducing sugars. The research demonstrates the process's efficiency and stereoretention with various monosaccharides, disaccharides, and trisaccharides, including those with fluorinated substrates to enhance the anomeric effect. The method's scalability is also validated, and it is suggested that this strategy could be broadly applicable for constructing complex acetals in carbohydrate chemistry.
10.1021/acscatal.9b01535
The research focuses on the development of a novel and cost-effective asymmetric transfer hydrogenation (ATH) catalyst system using ruthenium (Ru) complexes with minimal stereogenicity. The study introduces a series of Ru-catalysts, denoted as B1-B12, which feature a single stereogenic element derived from (1-pyridine-2-yl)methanamine ligands. These catalysts were designed to simplify existing protocols and demonstrate high levels of stereoinduction across a broad range of ketone substrates, including those challenging for known catalyst systems. The experiments involved the use of achiral diphosphines and (1-(pyridine-2-yl)methanamine derivatives as reactants, with 2'-chloroacetophenone as a model substrate. The catalysts were evaluated under mild transfer hydrogenation conditions using isopropanol (iPrOH) as the hydrogen source and potassium tert-butoxide (BuOK) as the base. The performance of each catalyst was analyzed in terms of yield and enantioselectivity (ee), with catalyst B10 showing the highest enantioselectivity of up to 91% ee. The study also explored the synthetic utility of the new catalysis protocol in a three-step preparation of a chiral (1-(pyridine-2-yl)methanamine ligand in its enantio-pure form, highlighting the economic and efficiency advantages over traditional methods.
10.1021/acs.orglett.1c00515
The research aims to disclose an efficient synthetic method for N-arylphenothiazines from o-sulfanylanilines without the use of transition metals. The study focuses on an N- and S-arylation sequence that enables the synthesis of a wide variety of N-arylphenothiazines, including the one-pot synthesis from readily available modules. Key chemicals used in the process include o-sulfanylanilines, aryne intermediates, potassium t-butoxide in N,N-dimethylacetamide (DMA), and various substituted o-sulfanylanilines. The research concludes that the ortho arylthio group in o-sulfanylanilines acts as a masked thiolate and an aryl donor moiety for N-arylation, and that the aromatic rings do not require activation by electron-withdrawing groups for the efficient N- and S-arylation sequence. The method expands the scope of available N-arylphenothiazines, which are significant in medicinal chemistry, materials science, and as photoredox catalysts, organic semiconductor compounds, and fluorescent compounds.
10.1021/jo00227a025
The research investigates whether the Cannizzaro reaction, a fundamental organic chemistry reaction involving aldehydes without α-hydrogen atoms and a strong base to form an equimolar mixture of the corresponding alcohol and carboxylic acid salt, proceeds at least to some extent by a single-electron-transfer (SET) mechanism. The study utilized ESR spectroscopy to identify substituted benzaldehyde radical anions produced in the reactions and correlated these ESR-active species with product formation. The results indicated that under the conditions studied, the Cannizzaro reaction often yielded high yields of products and isolated dimeric products, which are likely formed through a radical process. Chemicals used in the process included various substituted benzaldehydes, NaOH, KO-t-Bu, the THF/HMPA solvent system, and N-tert-butyl-α-phenylnitrone as a radical trap. The research concluded that the evidence supports the involvement of SET mechanisms and the formation of radical intermediates in the Cannizzaro reaction, a finding that challenges previous assumptions about the reaction pathway.
10.1039/c39800000884
The research investigates intramolecular nucleophilic substitutions of coordinated aryl halides to prepare chromans. The key chemicals involved include 3-(0-fluorophenyl)propan-1-ol, chromium tricarbonyl complexes, (η?-benzene)(+ethyl-tetramethylcyclopentadienyl)rhodium(III) cation, potassium t-butoxide, and boron trifluoride-ether. The study found that coordination with a chromium tricarbonyl residue significantly enhances the rate of intramolecular nucleophilic substitution. The hexafluorophosphate(V) salt of the complexed rhodium(III) cation was also used to catalyze the cyclizations of fluoro alcohols to chromans under mild conditions. However, attempts to use these systems for the preparation of five-membered oxygen heterocycles were unsuccessful, likely due to the strain associated with the bicyclic intermediate.
10.1021/jo00317a030
The study investigates the synthesis and properties of substituted 2,6-dioxabicyclo[3.1.1]heptanes, specifically focusing on the compounds 1,3-anhydro-2,4,6-tri-O-benzyl-β-D-mannopyranose and 1,3-anhydro-2,4,6-tri-O-(p-bromobenzyl)-β-D-mannopyranose. These compounds are synthesized through a series of reactions involving various reagents such as dibutyltin oxide, allyl bromide, benzyl chloride, and p-bromobenzyl bromide. The synthesis process includes steps like acetylation, benzylation, and ring closure using strong bases like sodium hydride (NaH) and potassium tert-butoxide (t-BuOK). The study aims to produce these anhydro sugars as precursors for the synthesis of 1,3-mannopyranans by ring-opening polymerizations, which are of interest for their potential applications in immunological and biochemical investigations. The compounds' structures are confirmed through mass spectrometry, 1H NMR, and 13C NMR spectroscopy, and their stability and purity are assessed through various analytical techniques.
10.2174/157017809790443005
The study presents a new method for preparing N-tosyl-L-phenylalanine chloromethyl ketone (TPCK), an irreversible serine protease inhibitor, without using toxic and explosive diazomethane. L-Phenylalanine is first tosylated to form N-tosyl-L-phenylalanine, which is then converted into its 4-nitrophenyl ester using DCC and DMAP. This ester reacts with dimethylsulfoxonium methylide, generated from trimethylsulfoxonium iodide and potassium tert-butoxide, to form a sulfur ylide. The sulfur ylide is subsequently treated with lithium chloride and methanesulfonic acid to produce the chloroketone, TPCK. This method achieves an overall yield of 36% and avoids the use of hazardous diazomethane, providing a safer and practical synthesis route.
10.3987/COM-96-7700
The research aims to synthesize 3-amino-2(1H)-quinolones and heterocondensed 2(1H)-pyridones through the cyclization of N-acylated anthranilic acid derivatives using the Thorpe-Ziegler cyclization method. The purpose of this study is to develop a more efficient route to synthesize these compounds, which are known as AMPA- and NMDA-receptor antagonists and are considered for the treatment of neurodegenerative diseases. The key chemicals used in the research include N-iodoacetylated anthranilic acid derivatives, secondary amines, and potassium tert-butoxide in dimethyl sulfoxide as the basic catalytic system. Potassium tert-butoxide (KOtBu) plays a crucial role as a strong base in the Thorpe-Ziegler cyclization process. Its primary function is to deprotonate the methylene group adjacent to the nitrile group in the N-acylated anthranilic acid derivatives, thereby activating it for cyclization. The researchers found that even electron-donor substituted methylene groups can undergo the Thorpe-Ziegler cyclization under relatively mild conditions, which was previously unreported. The study successfully synthesized various 3-amino-2(1H)-quinolones and heterocondensed 2(1H)-pyridones with different substitution patterns. However, pharmacological studies on the synthesized compounds did not reveal significant anticonvulsive activity. The research concludes that the Thorpe-Ziegler cyclization is a versatile method for synthesizing amino-substituted heterocycles, expanding the scope of accessible compounds through this reaction.
10.1021/acs.orglett.0c02635
The study presents the development of a catalytic system for the C-alkylation of N-heterocyclic compounds, such as pyridine, pyrimidine, pyrazine, quinoline, quinoxaline, and isoquinoline, using alcohols. The process is based on a hydrogen-borrowing approach and utilizes [Cp*IrCl2]2 as the catalyst precursor, combined with potassium t-butoxide and 18-crown-6-ether. This method is environmentally friendly as it only produces water as a byproduct. The researchers optimized the reaction conditions and demonstrated the system's versatility by applying it to various substrates, achieving good to excellent yields. The study also proposed a possible reaction mechanism involving three steps: hydrogen transfer from alcohol to iridium catalyst, cross-aldol-type condensation, and transfer hydrogenation. The developed catalytic system is expected to contribute to the synthesis of pharmaceuticals and functional materials.
10.1039/c2nj40194k
The research focuses on the synthesis, characterization, and investigation of a series of poly(p-phenylenevinylene) (PPV) based polymers, specifically MEH-OXD-PPVs, which are functionalized with Y-shaped double 1,3,4-oxadiazole-containing side chains. The polymers were synthesized through a modified Gilch reaction and were found to be soluble in common organic solvents. The chemical structures were confirmed using 1H NMR, GPC, and elemental analysis. The polymers exhibited good thermal stability with decomposition temperatures ranging from 312°C to 326°C as determined by thermogravimetric analysis. The optical properties, including absorption and fluorescence emission, were analyzed and showed a blue-shift with the increase of oxadiazole-containing moieties. Electrochemical investigation revealed that the HOMO energy levels varied with the content of oxadiazole-containing moieties. The PL quantum efficiencies were significantly enhanced by introducing more OXD-PV units during copolymerization. The experiments utilized various reactants such as N-bromosuccinimide, potassium tert-butoxide, and different monomers, while analyses included 1H NMR for structural confirmation, GPC for molecular weight determination, and cyclic voltammetry for electrochemical properties.