946-38-3Relevant articles and documents
Unprecedented Highly cis-Diastereoselective Olefin Cyclopropanation Using Copper Homoscorpionate Catalysts
Requejo-Diaz, Mar M.,Belderrain, Tomas R.,Trofimenko, Swiatoslaw,Perez, Pedro J.
, p. 3167 - 3168 (2001)
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Novel efficient catalysts based on imine-linked mesoporous polymers for hydrogenation and cyclopropanation reactions
Verde-Sesto, Ester,Maya, Eva M.,Lozano, Angel E.,De La Campa, Jose G.,Sanchez, Felix,Iglesias, Marta
, p. 24637 - 24643 (2012)
Two imine-linked polymer organic frameworks (POFs) with different geometries (C3v-POF and Th-POF) and mesoporous properties were prepared and proved to be catalyst supports. Due to the greater ability of Th-POF to coordinate metals, Cu- and Ir-coordinated
Transition metal-catalyzed cyclopropanation of alkenes in fluorinated alcohols
Azzouzi-Zriba, Kaouther,Bonnet-Delpon, Danile,Crousse, Benoit
, p. 811 - 814 (2011)
The system hexafluoroisopropanol/ethyl diazoacetate/Cu(OTf)2 is efficient for the cyclopropanation reaction. The process is experimentally simple, and efficient with various olefins in particular terminal, disubstituted double bonds.
New polymers for catalytic carbene transfer: Electropolymerization of tetrafluorenylporphyrinruthenium carbon monoxide
Paul-Roth, Christine,Rault-Berthelot, Jo?lle,Simonneaux, Gérard
, p. 12169 - 12175 (2004)
Condensation of pyrrole with 2-fluorenecarboxaldehyde yields meso-tetrafluorenylporphyrin as a new building block. After ruthenium insertion, oxidative electropolymerization of tetrafluorenylporphyrinruthenium (II) carbonyl complexes can be used to coat P
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.
Selective carbene transfer to amines and olefins catalyzed by ruthenium phthalocyanine complexes with donor substituents
Cailler, Lucie P.,Kroitor, Andrey P.,Martynov, Alexander G.,Gorbunova, Yulia G.,Sorokin, Alexander B.
supporting information, p. 2023 - 2031 (2021/02/26)
Electron-rich ruthenium phthalocyanine complexes were evaluated in carbene transfer reactions from ethyl diazoacetate (EDA) to aromatic and aliphatic olefins as well as to a wide range of aromatic, heterocyclic and aliphatic amines for the first time. It was revealed that the ruthenium octabutoxyphthalocyanine carbonyl complex [(BuO)8Pc]Ru(CO) is the most efficient catalyst converting electron-rich and electron-poor aromatic olefins to cyclopropane derivatives with high yields (typically 80-100%) and high TON (up to 1000) under low catalyst loading and nearly equimolar substrate/EDA ratio. This catalyst shows a rare efficiency in the carbene insertion into amine N-H bonds. Using a 0.05 mol% catalyst loading, a high amine concentration (1 M) and 1.1 eq. of EDA, a number of structurally divergent amines were selectively converted to mono-substituted glycine derivatives with up to quantitative yields and turnover numbers reaching 2000. High selectivity, large substrate scope, low catalyst loading and practical reaction conditions place [(BuO)8Pc]Ru(CO) among the most efficient catalysts for the carbene insertion into amines.
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.
