Refernces
10.1007/s10593-010-0647-2
The study focuses on the intramolecular cyclization of 1-[1-alkylsulfanyl-2-phenyl-2-(phenylhydrazono)ethylidene]pyrrolidinium salts, which are synthesized by the alkylation of thioamide with benzyl, allyl, and propargylsulfanyl groups in the presence of cesium carbonate in DMF at room temperature. These pyrrolidinium salts can be efficiently converted into 1,3-diphenyl-6,7,8,8a-tetrahydro-1H-pyrrolo[2,1-c]-1,2,4-triazine-4-thione derivatives in good yields. The research demonstrates that this cyclization method is general for alkyl derivatives of arylhydrazonothioacetamides, expanding the scope of this reaction type. The synthesized pyrrolotriazines are of practical interest due to their potential high antitumor activity, making them promising candidates for biological investigation. The study was financially supported by the Russian Basic Research Fund and includes detailed experimental procedures, characterization data, and comparison of the reaction outcomes with different bases and solvents.
10.1016/j.tet.2015.10.002
The study presents a facile and general method for synthesizing 2,5,7-trisubstituted indoles, which are significant in pharmaceuticals and natural compounds due to their biological activity. The researchers utilized a one-pot Sonogashira cross-coupling reaction followed by a palladium-catalyzed cyclization to construct the indole rings from readily available 2-bromo-6-iodo-4-substituted and 2-bromo-4-chloro-6-iodoanilines. Further functionalization at the C7 and C5 positions was achieved through alkynylations, Suzuki-Miyaura cross-couplings, and Buchwald-Hartwig C-N bond forming reactions. The methodology offers high yields, simplicity, and versatility, making it valuable for the synthesis of biologically active compounds. The study also includes one-pot protocols for the synthesis of these complex indole derivatives, enhancing the efficiency of the process.
10.1016/j.tetlet.2004.09.136
The study focuses on the reactivity of substituted pyridinium N-(20-azinyl)aminides in the Suzuki–Miyaura cross-coupling reaction, a widely used method for forming sp2–sp2 carbon–carbon bonds. The researchers investigated the coupling of these compounds with various boronic acids, using Cs2CO3 as a base, which resulted in good yields and substitution on the negatively charged moiety. They optimized the reaction conditions and found that the process was efficient for a range of substrates, including those with electron-deficient diazine rings, albeit requiring longer reaction times. The study also explored a double Suzuki process with a dibromoaminide to yield diarylated ylides. The results provide a valuable strategy for the synthesis of functionalized 2-aminoazines, which are important in medicinal and heterocyclic chemistry, and the researchers are continuing their efforts to expand the application of this process to other N-aminides.
10.1071/CH16710
The study reports on the successful synthesis and characterization of two 28-membered, 2,2'-bipyridine-containing macrocycles in high yield. The first macrocycle was formed through a Williamson ether synthesis, and upon reduction with sodium borohydride, the second macrocycle was produced quantitatively. These macrocycles, which contain a 2,2'-bipyridine unit, are potentially useful components for creating a variety of interlocked architectures, including catenanes, rotaxanes, and molecular machines. The research builds upon previous work by Sauvage, Stoddart, and Feringa, who were awarded the 2016 Nobel Prize in Chemistry for their contributions to the design and synthesis of molecular machines, and it aims to improve upon the yield-limiting macrocyclisation reactions that have historically been a challenge in the field. The study also discusses the use of high-yielding synthetic strategies and the potential for future investigations into the metal-complexation properties of these ligands and their application in forming interlocked structures.
10.1021/ja2039248
This study focuses on the Pd-catalyzed cross-coupling of racemic tertiary allylic carbonates and allylic boronic esters, leading to the enantioselective construction of all-carbon quaternary centers. The process is highly regio- and enantioselective, overcoming challenges associated with the formation of crowded carbon centers and reduced steric bias between enantioplanes. The study explores the reaction mechanism, which is believed to proceed via a 3,30-reductive elimination of a bis(η1-allyl)palladium intermediate. The experiments involved the optimization of reaction conditions using various additives such as Cs2CO3 and CsF and solvent systems, with the best conditions being CsF (3 equiv) and a 10:1 THF/H2O solvent system. A range of substrates were tested, including aromatic tertiary allylic carbonates, oxygen- and halogen-substituted substrates, and aliphatic substrates, and the reaction showed tolerance to a variety of substitution patterns. Analytical techniques used to distinguish product olefins and evaluate reaction efficiency include 1H NMR analysis for product ratios, chiral GC, SFC, or HPLC analysis (for enantiomeric ratios), and various synthetic applications to demonstrate the utility of the developed method.
10.1039/c9sc06184c
The research focuses on the development of a redox-neutral photochemical Heck-type arylation of vinylphenols activated by visible light. The study discloses a method for the arylation of vinylphenols with non-activated aryl and heteroaryl halides under visible light irradiation, utilizing colored vinylphenolate anions as strong reducing photoactivators. These anions activate (hetero)aryl halides without the need for sacrificial reductants, leading to the formation of aryl radicals that couple with another molecule of vinylphenol to produce the desired arylation product in a regiospecific and stereoselective manner. The experiments involved the optimization of reaction conditions, evaluating the substrate scope with various (hetero)aryl halides, and conducting mechanistic investigations. Reactants included 4'-bromoacetophenone, methyl 4-hydroxycinnamate, and Cs2CO3 as the base, with DMSO as the solvent and blue LED light as the irradiation source. Analyses used to characterize the products and confirm the reaction mechanism included X-ray crystallography, UV-vis absorption spectra, Stern-Volmer quenching studies, and quantum yield determination.
10.1055/s-0036-1591995
The research focuses on the asymmetric synthesis of cyclopentene-fused tetrahydroquinoline derivatives using N-heterocyclic carbene (NHC) catalyzed domino reactions. The experiments involved a one-pot organocatalytic protocol utilizing readily available quinolinone and enal substrates, with Cs2CO3 as the base and toluene as the solvent. Various NHC precatalysts were screened to optimize reaction conditions, leading to high yields and excellent stereoselectivities. The study analyzed the reaction scope by testing different enals and tetrahydroquinolinone substrates, employing techniques such as HPLC for enantiomeric excess (ee) determination, NMR for product characterization, and X-ray crystallography for confirming the absolute configuration of the synthesized compounds.
10.1021/acs.orglett.8b01646
The research focuses on the development of switchable selectivity in Pd-catalyzed alkylative cross-coupling of esters with alkyl boranes, a significant advancement in constructing C(sp2)?C(sp2) and C(sp2)?C(sp3) bonds. The study discloses two reaction modes that can be selectively accessed by interchange of the catalyst, with a Pd?NHC system leading to the formation of alkyl ketones via a Suzuki?Miyaura reaction by activating the C(acyl)?O bond, and a Pd?dcype catalyst enabling the synthesis of alkylated arenes through a modified pathway with extrusion of CO. The purpose of this research was to extend the impact and utility of the Suzuki?Miyaura reaction by enabling the formation of more diverse products from simple starting materials, and to control the selectivity in cross-couplings of esters, which remains a considerable challenge. The chemicals used in the process include phenyl esters, alkyl boranes, cesium carbonate, water, toluene, and various palladium catalysts with different ligands. The conclusions drawn from the research indicate that the divergent coupling strategy allows for the transformation of a single starting material into different classes of products, which is particularly powerful for the preparation of diverse, potentially bioactive molecules.
10.1021/ol8029627
The study presents an efficient method for nucleophilic fluoromethylation of alkyl and benzyl halides using fluorobis(phenylsulfonyl)methane (1) as a versatile reagent. The researchers achieved stereospecific one-pot synthesis of fluorovinyl compounds such as fluorostyrylsulfones, fluorocinnamates, and fluorochalcones using benzyl halides. The methodology was extended to synthesize R-substituted fluoroalkane derivatives through selective reductive desulfonylation. The study highlights the importance of fluorine in modifying the physicochemical and pharmacokinetic properties of drug molecules. The researchers used mild bases like potassium carbonate in DMF or cesium carbonate in acetonitrile to generate the soft carbanion [R-fluorobis(phenylsulfonyl)methide] from R-fluorobis(phenylsulfonyl)methane, which then reacted with primary alkyl iodides and bromides to produce alkylated products in moderate to excellent yields. For benzyl halides, the reaction led to the formation of fluorovinyl sulfones, indicating a second elimination step. The study also explored reductive desulfonylation using a Mg/HOAc/NaOAc system for monodesulfonylation and a Mg/MeOH system for didesulfonylation, yielding R-fluoro-R-(phenylsulfonyl)alkanes and R-fluoroalkanes, respectively.