10.1016/S0040-4039(01)01862-7
The study focuses on the chemoselective reduction of the imino (C≡N) bond in a series of oximino ethers using zirconium tetrachloride-sodium borohydride reagent, aiming to synthesize O,N-disubstituted hydroxylamines without cleaving the N-O bond. The researchers observed that precomplexation with zirconium cation in ether-methylene chloride solutions was effective for selective C≡N bond reduction, and the stereochemical control was dictated by Lewis acid coordination complexes of E- and Z-oximino ethers, leading to the preferred diastereofacial delivery of external hydride. Key chemicals used in the study include zirconium tetrachloride (ZrCl4), sodium borohydride (NaBH4), diethyl ether (Et2O), and methylene chloride (CH2Cl2), which served to facilitate the reduction reaction and control the stereochemistry of the products. The study also involved the use of various oximino ethers as substrates for the reduction, and the products were characterized by their yields and diastereomeric ratios, indicating the selectivity and stereochemical control achieved in the reactions.
10.1016/j.bmc.2011.07.056
The research focuses on the design and synthesis of 1,3-biarylsulfanyl derivatives as potential new anti-breast cancer agents. The purpose of this study was to develop novel estrogen receptor ligands by modifying the benzothiophene core of raloxifene, a known selective estrogen receptor modulator (SERM), to create secoraloxifene scaffolds. The synthesized compounds were screened for their anti-proliferative, anti-osteoporotic, and anti-implantation activities. The research concluded that certain compounds, particularly those with basic amino anti-estrogenic side chains (35, 36), showed significant anti-proliferative activity in various cancer cell lines and also exhibited anti-osteoporotic activity comparable to raloxifene. The chemicals used in the synthesis process included substituted chalcones, mercaptans, zirconium chloride as a catalyst, and various alkyl thiols and alkylamines for the introduction of the antiestrogenic side chain. The study suggests that these 1,3-biarylsulfanyl derivatives could be potential candidates for the treatment of breast cancer and osteoporosis.
10.1021/jo9903398
The research aimed to develop diastereo- and enantioselective synthetic methods for α-amino cyclic ethers. These compounds are significant due to their presence in marine natural polycyclic ethers. The study focused on the intramolecular reaction of γ-alkoxyallylstannanes with imines, using various Lewis acids and chiral catalysts. The researchers successfully achieved high diastereoselectivity in the synthesis of trans α-amino cyclic ethers using nonchiral and chiral auxiliary approaches. They also developed the first asymmetric synthesis of α-amino cyclic ethers using a chiral titanium-BINOL complex, achieving high enantioselectivity. Key chemicals used in the process included γ-alkoxyallylstannanes, imines, Lewis acids such as TiCl2(OiPr)2 and ZrCl4, and chiral catalysts like the titanium-BINOL complex.
10.1021/ja101994q
The research details the total synthesis of (-)-anominine, a biologically active diterpenoid compound. The synthesis involves the use of several key chemicals and transformations. The process begins with an asymmetric Robinson annulation of dione 2 using N-Ts-(Sa)-binam-L-Pro as a catalyst to create quaternary stereogenic centers. The enantioenriched intermediate 3 is then used in a conjugated addition reaction to form compound 4. A Wittig methylenation and subsequent oxidation with IBX in the presence of TsOH lead to the formation of endocyclic enone 6. The lithium enolate of 6 reacts with Eschenmoser’s salt and undergoes m-CPBA oxidation to yield the exocyclic enone, which is reduced to obtain stereochemically pure 7. Further reductions and rearrangements, including a sigmatropic rearrangement in a wet medium, lead to the key intermediate 9. The synthesis continues with selective transformations, including hydroboration, hydrogenation, and acetylation, followed by allylic oxidation and Dess-Martin oxidation to form 12. The final steps involve coupling with zirconium tetrachloride, oxidation with Ley’s perruthenate, Wittig bishomologation, and olefin cross-metathesis to achieve the target compound (-)-anominine. The success of the synthesis relies on chemoselective transformations controlled by the structurally congested nature of the bicyclic core and the development of an efficient method for synthesizing Wieland-Miescher ketone compounds.
10.1021/acs.inorgchem.9b00259
The research presents the synthesis and application of a new Zr(IV)-based urea-functionalized UiO-67 metal-organic framework (MOF) as a heterogeneous catalyst for the Friedel-Crafts alkylation of indole with ?-nitrostyrene. The MOF, designated as 1', was prepared using a urea-functionalized biphenyl-4,4'-dicarboxylic acid (BPDC-urea) linker and thoroughly characterized. It exhibited a high BET surface area and demonstrated excellent catalytic activity, achieving a 97% yield in the Friedel-Crafts alkylation reaction under optimized conditions (toluene, 70 °C, 24 hours). ZrCl4 (Zirconium Tetrachloride) is a white crystalline solid that is highly reactive. It is used to form the [Zr6O4(OH)4]12+ secondary building units (SBUs) that are essential for the framework structure of the UiO-67 MOF. The research underscores the potential of urea-functionalized MOFs as efficient and reusable catalysts for organic synthesis.