619-44-3Relevant academic research and scientific papers
Flexible bifunctional monoethylphosphonate/carboxylates of Zn(ii) and Co(ii) reinforced with DABCO co-ligand: paradigmatic structural organization withpcutopology
Boldog, Ishtvan,G?kpinar, Serkan,Gil-Hernández, Beatriz,Goldman, Anna,Heering, Christian,Janiak, Christoph,Millan, Simon
, p. 2933 - 2944 (2020)
Two novel isostructural phosphonate-monoethylcarboxylate MOFs with the structural formula of [M2(EtBCP)2(DABCO)0.5]·2DMA (M = Zn (2), Co (3); H2EtBCP =O-ethyl-P-(4-carboxyphenyl)phosphonic acid, DABCO = 1,4-diazabicyclo[2.2.2]octane, DMA =N,N-dimethylacetamide) were synthesized and characterized. The frameworks of2and3are sustained by {Zn2(PO2(OEt))2}nmetal-phosphonate- and DABCO-extended {Zn2(COO)4(DABCO)}npaddle-wheel carboxylate chain-SBUs. The chains providing connectivity in three, mutually orthogonal directions are running parallel and are combined in a framework, which could be interpreted as having apcutopology. The simple structure-organization principle, which suggests the possibility of the elongation of the bifunctional ligand with scaling in two directions, allows to view the structures of2and3as prototypes for an isoreticular series. The porosity of both compounds, based on a relatively short ligand, is low: no adsorption of N2was registered, however, CO2is adsorbed readily allowing to estimate the surface area at ～330 m2g?1(～900-1060 m2g?1geometric estimate). The compounds demonstrate a two-step CO2adsorption isotherm both at 195 K (0-1 bar) and 298 K (0-20 bar). The adsorption isotherms are characterized by a gradual (type “F-I”), albeit still relatively steep onset of the second step, associated with structural flexibility/bistability. The estimated pore volumes at the start of the transformation (195 K) for2and3are ～0.11 (0.08P/P0) and 0.12 cm3g?1(0.12P/P0) respectively, which corresponds considerably well to the geometrically calculated accessible volume of ～0.07 cm3g?1for the experimental structure (3.3 ? probe diameter). The structural prerequisites of the observed flexibility of the framework, which might be associated with the non-planarity of the metal-phosphonate moieties, acting as ‘levers’ for propagating mechanical stress, are discussed.
Modular Generation of (Iodinated) Polyarenes Using Triethylgermane as Orthogonal Masking Group
Deckers, Kristina,Fricke, Christoph,Hupperich, Daniel,Kreisel, Tatjana,Mendel, Marvin,Queen, Adele E.,Riegger, Julian,Schoenebeck, Franziska
, (2022/03/31)
While the modular construction of molecules from suitable building blocks is a powerful means to more rapidly generate a diversity of molecules than through customized syntheses, the further evolution of the underlying coupling methodology is key to realize widespread applications. We herein disclose a complementary modular coupling approach to the widely employed Suzuki coupling strategy of boron containing precursors, which relies on organogermane containing building blocks as key orthogonal functionality and an electrophilic (rather than nucleophilic) unmasking event paired with air-stable PdI dimer based bond construction. This allows to significantly shorten the reaction times for the iterative coupling steps and/or to close gaps in the accessible compound space, enabling straightforward access also to iodinated compounds.
Field-induced single-ion magnets exhibiting tri-axial anisotropy in a 1D Co(ii) coordination polymer with a rigid ligand 4,4′-(buta-1,3-diyne-1,4-diyl)dibenzoate
C. Silva, Henrique,Ferreira, Glaucio B.,Guedes, Guilherme P.,Matos, Catiúcia R. M. O.,Nunes, Wallace C.,Ronconi, Célia M.,Sarmiento, Charlie V.
, p. 15003 - 15014 (2021/11/17)
Herein a 1D Co(ii) coordination polymer of formula [Co(η1-L1)(η2-L1)(py)2(H2O)]n (CoCP) has been synthesised using the rigid H2L1 proligand, containing a long spacer bearing two triple bonds. Single-crystal X-ray diffraction showed that Co(ii) adopts a distorted octahedral geometry. The state-averaged complete active self-consistent field (SA-CASSCF) calculation showed that the ground state of CoCP is a high spin quartet with a highly multiconfigurational character of its electronic structure. Due to the large intra- and intermolecular distances between the spin carriers, the magnetic interactions are negligible and the zero-field splitting (ZFS) effects of cobalt(ii) ions are predominant. This behavior was confirmed by direct current (DC) magnetic measurements and theoretical calculations using the broken-symmetry approach. Quantum chemical calculations indicate that CoCP has a negative axial component possessing mixed tri-axial anisotropy. The DC magnetic susceptibility data were fitted with a Griffith-Figgis Hamiltonian and the obtained parameters are in good agreement with those simulated by the ab initio calculation. Alternating current (AC) magnetic measurements showed a field induced slow magnetic relaxation in CoCP, which is attributed to the hyperfine interaction effects.
BODIPY compounds containing 8-(diphenylethynyl)-ester groups as well as synthesis and application thereof
-
Paragraph 0034-0038, (2021/02/06)
The invention discloses BODIPY compounds containing 8-(diphenylethynyl)-ester groups as well as a preparation method and application thereof. The BODIPY compounds have a structure A. According to theinvention, BODIPY is used as a matrix, a diphenylacetylene rigid structure and an ester-based alkyl chain flexible structure are introduced to the No. 8 site through the Sonogashira coupling reaction,and a series of 8-(diphenylethynyl)-ester-based BODIPY dichroic dyes are designed and synthesized. The maximum emission wavelength of the compounds in dichloromethane is concentrated at about 518 nm,green fluorescence is shown, and good dichroic ratio and ordered parameters are shown in a liquid crystal E7; and the liquid crystal compounds provided by the invention have a liquid crystal mesophase within a temperature range of 50-100 DEG C, can be used for manufacturing liquid crystal display products, and particularly can be used as guest body dyes for guest-host mode liquid crystal displays; and when the compounds are added into the E7 liquid crystal and used in a guest-host display mode, response time can be prolonged, and the effect of quick response is achieved.
Palladium-Catalyzed Decarbonylative Iodination of Aryl Carboxylic Acids Enabled by Ligand-Assisted Halide Exchange
Boehm, Philip,Cacherat, Bastien,Lee, Yong Ho,Martini, Tristano,Morandi, Bill
supporting information, p. 17211 - 17217 (2021/07/02)
We report an efficient and broadly applicable palladium-catalyzed iodination of inexpensive and abundant aryl and vinyl carboxylic acids via in situ activation to the acid chloride and formation of a phosphonium salt. The use of 1-iodobutane as iodide source in combination with a base and a deoxychlorinating reagent gives access to a wide range of aryl and vinyl iodides under Pd/Xantphos catalysis, including complex drug-like scaffolds. Stoichiometric experiments and kinetic analysis suggest a unique mechanism involving C?P reductive elimination to form the Xantphos phosphonium chloride, which subsequently initiates an unusual halogen exchange by outer sphere nucleophilic substitution.
Method for preparing iodo-benzoic acid (ester) by improving moral Michael reaction
-
Paragraph 0024; 0037-0038, (2021/11/03)
The invention discloses a method for preparing iodo-benzoic acid (ester) by improving a moral reaction, and belongs to the technical field of organic synthesis. The method comprises the following steps: preparing and separating the diazonium tetrafluoroborate through diazotization of aminobenzoic acid (ester) and then performing iodination reaction with the iodinated reagent in an organic medium to obtain the corresponding iodo carboxylic acid (ester). The iodo-benzoic acid (ester) prepared by the method has high purity. The method has the advantages of good quality and simple post-treatment, and the product yield reaches 70 - 90%.
Mild Copper-Catalyzed Addition of Arylboronic Esters to Di- tert -butyl Dicarbonate: An Easy Access to Methyl Arylcarboxylates
Xu, Jin-Di,Su, Xiao-Bo,Wang, Cai,Yao, Li-Wei,Liu, Jing-Hui,Hu, Guo-Qin
supporting information, p. 833 - 837 (2021/02/26)
An efficient copper-catalyzed addition of arylboronic esters to (Boc) 2O was developed. The reaction can be conducted under exceedingly mild conditions and is compatible with a variety of synthetically relevant functional groups. It therefore represents a useful alternative route for the synthesis of methyl arylcarboxylates. A preliminary mechanistic study indicated the involvement of an addition-elimination mechanism.
Discovery of [1,2,4]triazole derivatives as new metallo-β-lactamase inhibitors
Yuan, Chen,Yan, Jie,Song, Chen,Yang, Fan,Li, Chao,Wang, Cheng,Su, Huiling,Chen, Wei,Wang, Lijiao,Wang, Zhouyu,Qian, Shan,Yang, Lingling
, (2020/01/11)
The emergence and spread of metallo-β-lactamase (MBL)-mediated resistance to β-lactam antibacterials has already threatened the global public health. A clinically useful MBL inhibitor that can reverse β-lactam resistance has not been established yet. We here report a series of [1,2,4]triazole derivatives and analogs, which displayed inhibition to the clinically relevant subclass B1 (Verona integron-encoded MBL-2) VIM-2. 3-(4-Bromophenyl)-6,7-dihydro-5H-[1,2,4]triazolo [3,4-b][1,3]thiazine (5l) manifested the most potent inhibition with an IC50 (half-maximal inhibitory concentration) value of 38.36 μM. Investigations of 5l against other B1 MBLs and the serine β-lactamases (SBLs) revealed the selectivity to VIM-2. Molecular docking analyses suggested that 5l bound to the VIM-2 active site via the triazole involving zinc coordination and made hydrophobic interactions with the residues Phe61 and Tyr67 on the flexible L1 loop. This work provided new triazole-based MBL inhibitors and may aid efforts to develop new types of inhibitors combating MBL-mediated resistance.
Generation of Organozinc Reagents from Arylsulfonium Salts Using a Nickel Catalyst and Zinc Dust
Yamada, Kodai,Yanagi, Tomoyuki,Yorimitsu, Hideki
, p. 9712 - 9718 (2021/01/09)
Readily available aryldimethylsulfonium triflates react with zinc powder under nickel catalysis via the selective cleavage of the sp2-hybridized carbon-sulfur bond to produce salt-free arylzinc triflates under mild conditions. This zincation displays superb chemoselectivity and thus represents a protocol that is complementary or orthogonal to existing methods. The generated arylzinc reagents show both high reactivity and chemoselectivity in palladium-catalyzed and copper-mediated cross-coupling reactions.
Methoxylation of Acyl Fluorides with Tris(2,4,6-trimethoxyphenyl)phosphine via C-OMe Bond Cleavage under Metal-Free Conditions
Ishida, Takumi,Nishihara, Yasushi,Wang, Xiu,Wang, Zhenhua
, p. 7526 - 7533 (2020/06/27)
Acyl fluorides are subjected to methoxylation with tris(2,4,6-trimethoxyphenyl)phosphine (TMPP) to afford the corresponding methyl esters in good to excellent yields. This transformation is featured by C(sp2)-OMe bond cleavage under metal-free conditions. Unprecedented utilization of TMPP as a methoxylating agent realized the installation of an OMe group into the desired products.
