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.tetlet.2004.09.025
The study presents a novel approach for constructing quaternary centers on cycloalkane rings, which is a significant challenge in synthetic chemistry. The researchers utilized a combination of Birch reduction-allylation and Cope rearrangement on o-anisic acid derivatives to synthesize 2-acyl-3-cyclohexenone derivatives. They successfully generated rearrangement substrates and achieved high yields of 2-cyclohexenone products through thermal equilibration in 1,2-dichlorobenzene. Notably, the Cope rearrangement of a specific substrate resulted in the formation of a new quaternary center with excellent yield, marking the first example of such synthesis on a cycloalkenone ring via Cope rearrangement. This method could serve as a powerful tool for creating substituted 2-cyclohexenones, offering a potentially versatile synthetic intermediate with potential for 1,3-chirality transfer and access to enantiomerically pure products.
10.1016/j.tetasy.2010.07.011
The research focuses on the indium-mediated Reformatsky reaction of sugar lactones, specifically the synthesis of 2-deoxy-2-substituted-3-ulosonic acids, which are important for creating biologically active compounds and new biopolymers. The experiments involved the reaction of a mannose-derived lactone with various ethyl 2-bromo-alkanoates and 2-bromo-lactones in the presence of indium powder and under ultrasonic waves. Reactants included D-mannose-derived lactone, different bromo-alkanoates, and 2-bromo-lactones. Allyl bromide 22 was used in the indium-mediated allylation reaction to produce addition adduct 23. The analyses used to characterize the products comprised of techniques such as single crystal X-ray analysis, NMR spectroscopy, and mass spectrometry, which confirmed the stereochemistry at the newly created stereogenic center and provided information on the structure and purity of the synthesized ulosonic acid esters. The study proposed a mechanistic explanation for the reaction's stereoselectivity and discussed the potential applications of the synthesized branched chain sugars.
10.1016/S0040-4020(98)01096-5
The research aimed to develop a simple, direct, and efficient method for converting thioamides into thioesters, which are activated carboxylic acid derivatives with applications in synthetic chemistry. The study addressed the need for a reliable, multi-gram synthesis of thioesters and proposed a new route from thioamides that is mild, inexpensive, and experimentally straightforward. The method involved warming thioamides in an aqueous tetrahydrofuran (THF) solution containing an alkylating agent, leading to high yields and being scalable to multi-gram levels. The reactions were found to be tolerant of aryl ethers and acetals, and when volatile alkyl halides were used, products of approximately 95% purity could be obtained without chromatographic purification. Key chemicals used in the process included various thioamides, alkyl iodides, dialkyl sulfates, and activated alkyl bromides as alkylating agents, with methyl iodide (MeI), ethyl iodide (EtI), allyl bromide (allyl-Br), and benzyl bromide (BnBr) being specific examples. The study concluded that the developed method was effective for preparing thioesters from thioamides, offering a practical alternative to existing methods.
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.
10.1023/A:1023419530311
The study in the provided document investigates the reaction of quaternary ammonium salts with a 1,1-dimethylbut-2-yne-1,4-diyl common group with aqueous alkali. The research focuses on the intermediate formation of 1,2-cleavage products rather than 1,4-cleavage products. When both nitrogen atoms have allylic groups, a rearrangement followed by cleavage and substitution occurs, leading to the formation of methyl isopropyl ketones. Salts with two 3-methylbut-2-en-1-yl groups result in the cleavage of isoprene. The study also explores the reactions of 1,4-diammonium salts with two methyl substituents in the but-2yne-1,4-diyl common group under the influence of aqueous alkali, detailing the products and mechanisms involved in these chemical transformations.
10.1016/j.tetasy.2009.08.021
The research focuses on the total synthesis of marine polypropionates—siphonarienal, siphonarienone, and pectinatone—employing a desymmetrization strategy to create three consecutive stereogenic centers. The synthesis involves a series of chemical reactions starting from known precursors, utilizing reactants such as allyl bromide, LHMDS, LAH, 2,2-dimethoxypropane, CSA, Bn-Br, TsCl, Et3N, DMAP, LiAlH4, DDQ, and others as detailed in the experimental section. The synthesis steps include allylation, reductive ring opening, protection of hydroxyl groups, selective tosylation, reductive cleavage, and oxidation, among others. The synthesized compounds were analyzed using techniques like TLC, NMR, MS, and HRMS to confirm their structures and purities. The study also compares the efficiency of this strategy to previous methods, highlighting its advantage of creating three stereogenic centers in a single reaction, which is more efficient than the approximately 10 steps required by other methods.