10.1021/jo00378a028
The research focuses on the synthesis of ethyl 3,3-difluoroacrylate (6) and its subsequent Diels-Alder reaction with furan to produce difluorocyclohexadienol derivatives. The purpose of this study was to develop an efficient method for synthesizing ethyl 3,3-difluoroacrylate, a compound of interest for its potential to introduce fluorine atoms into organic molecules, and to explore its reactivity in the Diels-Alder reaction. The researchers successfully developed a synthesis route with an overall yield of 36%, starting from ethyl vinyl ether and dibromodifluoromethane. Key chemicals used in the process include ethyl vinyl ether, dibromodifluoromethane, ethanol, Caro's acid, m-chloroperoxybenzoic acid, and triethylamine. The study concluded that ethyl 3,3-difluoroacrylate is more reactive than methyl acrylate and that the Diels-Alder reaction with furan, although accompanied by decomposition, yielded a mixture of epimers, demonstrating the potential of this approach for synthesizing complex molecules with fluorine substitution.
10.1021/ol035270b
The research investigates the use of ethylene to promote intermolecular enyne metathesis between functional group-rich alkynes and vinyl ethers. The study found that ethylene not only enhances the reactivity of the process but also protects the catalyst, thereby increasing the applicability of the intermolecular reaction to problematic substrates. Key chemicals involved in the research include ethylene, which acts as a co-added alkene to improve reaction efficiency; vinyl ethers such as ethyl vinyl ether (EVE); and various alkynes, including thiol benzoates and butynyl derivatives. The second-generation Grubbs catalyst was used to facilitate the metathesis reactions. The study also explored different solvents like benzene and dichloromethane, and examined the effects of varying ethylene pressures and reaction conditions on the outcomes. The results showed that ethylene significantly increased the lifetime of the Fischer carbene complex and enabled the reaction to proceed at ambient temperature, even with substrates that were previously unreactive or poorly reactive.
10.1039/b805071f
The research focuses on the synthesis, redox properties, and coordination chemistry of three novel trifluoromethylated enaminones (L1H–L3H) with copper(II). The purpose of this study is to explore the potential of these ligands to form coordination complexes with copper(II) and to investigate their redox behavior, which could have applications in catalysis, magnetism, and materials science. The enaminone ligands were synthesized through a two-step process involving trifluoroacetylation of ethyl vinyl ether followed by an O–N exchange reaction with various amines. The copper(II) complexes were prepared by reacting the ligands with CuCl2·2H2O in methanol. The structures of the complexes were determined by single-crystal X-ray diffraction, revealing monomeric and dimeric forms. Electrochemical studies showed that the reduction processes of the complexes were different in dichloromethane and N,N-dimethylformamide, with copper(II) being directly reduced to copper(0) in the former and a copper(I) intermediate being more stable in the latter. The conclusions suggest that these enaminone ligands have potential for further development into heteromultinuclear complexes with interesting electro-magnetic properties.
10.1021/ja994209s
The research focuses on the development of a new method for constructing ortho ring-alkylated phenols, which are prevalent in natural products and have applications as antioxidants, anticorrosives, and anticancer agents. The purpose of this study was to devise a procedure that could synthesize a variety of these phenols in a single operation, overcoming the limitations of previous methods such as rearrangement, electrophilic substitution, lithiation, and halogenation. The researchers aimed to achieve this by utilizing the reduction of ortho O-acylated phenones to produce phenols with ortho saturated alkyl substituents. The chemicals used in this process include NaBH4 as a reducing agent, organomagnesium reagents (Grignard reagents), and organolithium reagents to initiate the cascade reaction. The researchers also used acetyl chloride and ethyl vinyl ether (EVE) in their experiments. The study provides a detailed table (Table 1) that outlines the scope of the procedure, showcasing various nucleophiles and reaction conditions that lead to different products. The research concludes with a summary of the procedure's salient features, including the use of o-OBOC substituted aryl ketones and aldehydes, and the role of metal or its corresponding salt in the conversion of intermediate C to D.
10.1021/ol006172i
This research focuses on the diastereoselective synthesis of 3,4-dimethoxy-7-morphinanone, a compound that could potentially serve as an intermediate in the synthesis of morphine. The study aims to develop an efficient method for introducing the C14 stereogenic center and constructing the C9-C10 bridge of the morphinan system, which are crucial for the enantiocontrolled synthesis of morphine. The researchers successfully resolved racemic 2-(2,3-dimethoxyphenyl)cyclohexen-1-ol into its enantiomers and transformed it into the desired 3,4-dimethoxy-7-morphinanone through a series of reactions involving vinyl acetate, ethyl vinyl ether, N-bromosuccinimide (NBS), peracids, Lewis acids, and other reagents.
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