97-71-2Relevant articles and documents
Electrochemical Ring-Opening Dicarboxylation of Strained Carbon-Carbon Single Bonds with CO2: Facile Synthesis of Diacids and Derivatization into Polyesters
Liao, Li-Li,Wang, Zhe-Hao,Cao, Ke-Gong,Sun, Guo-Quan,Zhang, Wei,Ran, Chuan-Kun,Li, Yiwen,Chen, Li,Cao, Guang-Mei,Yu, Da-Gang
supporting information, p. 2062 - 2068 (2022/02/10)
Diacids are important monomers in the polymer industry to construct valuable materials. Dicarboxylation of unsaturated bonds, such as alkenes and alkynes, with CO2 has been demonstrated as a promising synthetic method. However, dicarboxylation of C-C single bonds with CO2 has rarely been investigated. Herein we report a novel electrochemical ring-opening dicarboxylation of C-C single bonds in strained rings with CO2. Structurally diverse glutaric acid and adipic acid derivatives were synthesized from substituted cyclopropanes and cyclobutanes in moderate to high yields. In contrast to oxidative ring openings, this is also the first realization of an electroreductive ring-opening reaction of strained rings, including commercialized ones. Control experiments suggested that radical anions and carbanions might be the key intermediates in this reaction. Moreover, this process features high step and atom economy, mild reaction conditions (1 atm, room temperature), good chemoselectivity and functional group tolerance, low electrolyte concentration, and easy derivatization of the products. Furthermore, we conducted polymerization of the corresponding diesters with diols to obtain a potential UV-shielding material with a self-healing function and a fluorine-containing polyester, whose performance tests showed promising applications.
Catalytic cyclopropanation, antimicrobial, and DFT properties of some chelated transition metal(II) complexes
Ababneh, Taher S.,Al-Dawood, Lina A.,Al-Momani, Waleed M.,Hijazi, Ahmed K.,Taha, Ziyad A.
, (2020/12/25)
Transition Metal (II) complexes of general formula [MII(NH2C2H4NH2)3][B(C6F5)4]2 (1-6), where (M= Mn, Fe, Co, Ni, Cu, Zn) have been synthesized and characterized in the solid state and in solution using elemental, thermogravimetric analysis, EPR, 11B-NMR and IR spectroscopy. All complexes were used as catalysts for the cyclopropanation reaction with a variety of olefins. Excellent yields up to 93% were obtained using complex 5. All prepared complexes were used as anti-bacterial agents against different types of bacteria (Gram-negative and Gram-positive), and as anti-fungal agents. Complex 6 showed the highest activity with MIC value of 8 μg/mL against Staphylococcus aureus (Gram-positive bacteria), and of 16 μg/mL against candida albicans. To get more insights into their structural features, molecular geometries of all prepared complexes were fully optimized using density functional theory calculations at the M06-2X/6-311+G** level of theory.
Controlling the Activity of a Caged Cobalt-Porphyrin-Catalyst in Cyclopropanation Reactions with Peripheral Cage Substituents
Mouarrawis, Valentinos,Bobylev, Eduard O.,de Bruin, Bas,Reek, Joost N. H.
supporting information, p. 2890 - 2898 (2021/07/09)
In this study, three novel cubic cages were synthesized and utilized to encapsulate a catalytically active cobalt(II) meso-tetra(4-pyridyl)porphyrin guest. The newly developed caged catalysts (Co-G@Fe8(Zn-L ? 1)6, Co-G@Fe8(Zn-L ? 2)6 and Co-G@Fe8(Zn-L ? 3)6) can be easily synthesized and differ in exo-functionalization, which are either none, polar or apolar groups. This leads to a different polarity of the peripheral environment surrounding the cage, which affects the (relative) local concentration of the substrates surrounding the cage and hence indirectly influences the substrate availability of the catalysis embedded in the active site of the caged catalyst systems. The resulting increased local substrate concentrations give rise to higher catalytic activities of the respective caged catalyst in metalloradical catalyzed cyclopropanation reactions. Interestingly, the catalytic activity is the highest when the apolar cage catalyst (Co-G@Fe8(Zn-L ? 1)6) is used, and lowest with the polar analog (Co-G@Fe8(Zn-L ? 3)6). In addition, the catalytic activity of the cage without exo-functionalities (Co-G@Fe8(Zn-L ? 2)6) is nearly two times lower than that of Co-G@Fe8(Zn-L ? 1)6 and three times higher than that of Co-G@Fe8(Zn-L ? 3)6, which further demonstrates the effect of the peripheral functionalities on the cyclopropanation reaction.
