1575-61-7Relevant academic research and scientific papers
Synthesis and characterization of a Gd(III) based contrast agent responsive to thiol containing compounds
Carrera, Carla,Digilio, Giuseppe,Baroni, Simona,Burgio, Daniela,Consol, Simona,Fedeli, Franco,Longo, Dario,Mortillaro, Armando,Aime, Silvio
, p. 4980 - 4987 (2007)
A novel Gd(iii) complex with a modified DO3A-like chelating cage has been synthesized and characterized as a candidate contrast agent responsive to the concentration of free thiols in tissues (essentially represented by reduced glutathione, GSH). The novel compound (called Gd-DO3AS-Act) bears a flexible linker ending with a 2-pyridyl-dithio group, that can promptly react with free thiols (XSH) to form mixed disulfides of the form Gd-DO3AS-SX. Compound Gd-DO3AS-Act is characterized by a millimolar relaxivity as high as 8.1 mM -1 s-1 (at 20 MHz, 25 °C and pH 7.4). Upon reaction with GSH, the Gd-DO3AS-SG covalent adduct is formed and the millimolar relaxivity drops to 4.1 mM-1 s-1. Such a decrease in relaxivity is explained on the basis of the formation of an intramolecular coordinative bond between one of the glutathionyl carboxyl groups and the Gd(iii) centre, lowering the hydration state of the paramagnetic centre. 1H-NMR dispersion profiles together with 17O-NMR transverse relaxation time versus temperature profiles confirm that the hydration of the Gd(iii) centre is strongly reduced ongoing from Gd-DO3AS-Act to the Gd-DO3AS-SG adduct. The relaxivity difference brought about by the reaction of Gd-DO3AS-Act with GSH can be enhanced up to 60% in the presence of poly-β-cyclodextrin. This journal is The Royal Society of Chemistry.
Scalable Total Synthesis, IP3R Inhibitory Activity of Desmethylxestospongin B, and Effect on Mitochondrial Function and Cancer Cell Survival
Podunavac, Ma?a,Mailyan, Artur K.,Jackson, Jeffrey J.,Lovy, Alenka,Farias, Paula,Huerta, Hernan,Molgó, Jordi,Cardenas, Cesar,Zakarian, Armen
supporting information, p. 11278 - 11282 (2021/04/19)
The scalable synthesis of the oxaquinolizidine marine natural product desmethylxestospongin B is based on the early application of Ireland–Claisen rearrangement, macrolactamization, and a late-stage installation of the oxaquinolizidine units by lactam reduction. The synthesis serves as the source of material to investigate calcium signaling and its effect on mitochondrial metabolism in various cell types, including cancer cells.
Synthesis of N-trifluoromethyl amides from carboxylic acids
Flavell, Robert R.,Liu, Jianbo,Parker, Matthew F. L.,Toste, F. Dean,Wang, Sinan,Wilson, David M.
supporting information, p. 2245 - 2255 (2021/08/12)
Found in biomolecules, pharmaceuticals, and agrochemicals, amide-containing molecules are ubiquitous in nature, and their derivatization represents a significant methodological goal in fluorine chemistry. Trifluoromethyl amides have emerged as important functional groups frequently found in pharmaceutical compounds. To date, there is no strategy for synthesizing N-trifluoromethyl amides from abundant organic carboxylic acid derivatives, which are ideal starting materials in amide synthesis. Here, we report the synthesis of N-trifluoromethyl amides from carboxylic acid halides and esters under mild conditions via isothiocyanates in the presence of silver fluoride at room temperature. Through this strategy, isothiocyanates are desulfurized with AgF, and then the formed derivative is acylated to afford N-trifluoromethyl amides, including previously inaccessible structures. This method shows broad scope, provides a platform for rapidly generating N-trifluoromethyl amides by virtue of the diversity and availability of both reaction partners, and should find application in the modification of advanced intermediates.
Decarboxylative Borylation of mCPBA-Activated Aliphatic Acids
Wei, Dian,Liu, Tu-Ming,Zhou, Bo,Han, Bing
supporting information, p. 234 - 238 (2020/01/02)
A decarboxylative borylation of aliphatic acids for the synthesis of a variety of alkylboronates has been developed by mixing m-chloroperoxybenzoic acid (mCPBA)-activated fatty acids with bis(catecholato)diboron in N,N-dimethylformamide (DMF) at room temperature. A radical chain process is involved in the reaction which initiates from the B-B bond homolysis followed by the radical transfer from the boron atom to the carbon atom with subsequent decarboxylation and borylation.
Intramolecular Cyclization of Brominated Oxime Ether Promoted with Ytterbium(0) to the Synthesis of Cyclic Imines
Wang, Yiqiong,Huang, Fei,Zhang, Songlin
supporting information, p. 5178 - 5181 (2020/08/13)
The first utility of ytterbium(0) as a mediating-metal in the intramolecular cyclization of brominated oxime ether was reported in this paper. In contrast to the prior methods, the N–O bond was used as a receptor of nucleophilic reagent, rather than as a source of N-centered radicals. Cyclic imines were obtained in this one-pot reaction with a broad scope of substrates and feasible reaction conditions.
Photochemical generation of acyl and carbamoyl radicals using a nucleophilic organic catalyst: Applications and mechanism thereof
Balletti, Matteo,De Pedro Beato, Eduardo,Mazzarella, Daniele,Melchiorre, Paolo
, p. 6312 - 6324 (2020/08/24)
We detail a strategy that uses a commercially available nucleophilic organic catalyst to generate acyl and carbamoyl radicals upon activation of the corresponding chlorides and anhydrides via a nucleophilic acyl substitution path. The resulting nucleophilic radicals are then intercepted by a variety of electron-poor olefins in a Giese-type addition process. The chemistry requires low-energy photons (blue LEDs) to activate acyl and carbamoyl radical precursors, which, due to their high reduction potential, are not readily prone to redox-based activation mechanisms. To elucidate the key mechanistic aspects of this catalytic photochemical radical generation strategy, we used a combination of transient absorption spectroscopy investigations, electrochemical studies, quantum yield measurements, and the characterization of key intermediates. We identified a variety of off-the-cycle intermediates that engage in a light-regulated equilibrium with reactive radicals. These regulated equilibriums cooperate to control the overall concentrations of the radicals, contributing to the efficiency of the overall catalytic process and facilitating the turnover of the catalyst. This journal is
Monoterpenoid-based inhibitors of filoviruses targeting the glycoprotein-mediated entry process
Baev, Dmitriy S.,Maksyutov, Rinat A.,Mordvinova, Ekaterina D.,Pyankov, Oleg V.,Salakhutdinov, Nariman F.,Shcherbakov, Dmitriy N.,Shcherbakova, Nadezhda S.,Sokolova, Anastasiya S.,Tolstikova, Tatyana G.,Yarovaya, Olga I.,Zaykovskaya, Anna V.,Zybkina, Anastasiya V.
, (2020/09/09)
In this study, we screened a large library of (+)-camphor and (?)-borneol derivatives to assess their filovirus entry inhibition activities using pseudotype systems. Structure-activity relationship studies revealed several compounds exhibiting submicromolar IC50 values. These compounds were evaluated for their effect against natural Ebola virus (EBOV) and Marburg virus. Compound 3b (As-358) exhibited the good antiviral potency (IC50 = 3.7 μM, SI = 118) against Marburg virus, while the hydrochloride salt of this compound 3b·HCl had a strong inhibitory effect against Ebola virus (IC50 = 9.1 μM, SI = 31) and good in vivo safety (LD50 > 1000 mg/kg). The results of molecular docking and in vitro mutagenesis analyses suggest that the synthesized compounds bind to the active binding site of EBOV glycoprotein similar to the known inhibitor toremifene.
Method for simultaneously preparing 5-chlorovaleryl chloride and adipoyl chloride by using one-pot method
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Paragraph 0017; 0018; 0019; 0020; 0021; 0022; 0023-0028, (2018/07/30)
The invention discloses a method for simultaneously preparing 5-chlorovaleryl chloride and adipoyl chloride by utilizing a one-pot method. The method comprises the following steps: 1,4-dichlorobutaneis taken as a raw material, in the presence of a phase transfer catalyst, an aqueous solution of sodium cyanide is gradually added dropwise into a reaction kettle, and therefore a 1,4-dichlorobutane solution of 5-chlorovaIeronitrile and adiponitrile is obtained; the obtained organic phase and aqueous phase are separated, hydrolysis is performed, and therefore a 1,4-dichlorobutane solution of 5-chlorovaleric acid and adipic acid is obtained; water is added into the obtained ammonium chloride solid until the solid is completely dissolved, and an aqueous phase is separated; thionyl chloride is added into the obtained 1,4-dichlorobutane solution of 5-chlorovaleric acid and adipic acid for an acylating chlorination reaction, and therefore a 1,4-dichlorobutane solution of 5-chlorovaleryl chloride and adipoyl chloride is obtained; and the obtained 1,4-dichlorobutane solution of 5-chlorovaleryl chloride and adipoyl chloride is put into a vacuum rectification tower for vacuum rectification, andtherefore the adipoyl chloride product with the distillate temperature of 105 DEG C-107 DEG C is obtained through distillation. The method provided by the invention adopts the 1,4-dichlorobutane as the raw material and adopts the ''one-pot method'' to simultaneously produce the two intermediate products 5-chlorovaleryl chloride and adipoyl chloride, and the method has a high yield, large single-pot production capacity, a small solvent circulation amount, low energy consumption, and less ''three wastes'' (waste gas, waste water and solid waste).
Palladium-catalyzed allylic alkylation of carboxylic acid derivatives: N-acyloxazolinones as ester enolate equivalents
Trost, Barry M.,Michaelis, David J.,Charpentier, Julie,Xu, Jiayi
supporting information; experimental part, p. 204 - 208 (2012/02/16)
Triple A: A general asymmetric allylic alkylation of ester enolate equivalents at the carboxylic acid oxidation state is reported. N-Acylbenzoxazolinone-derived enol carbonates were synthesized and employed in the palladium-catalyzed alkylation reaction. The imide products were readily converted into a series of carboxylic acid derivatives without loss of enantiopurity.
Synthesis and radiofluorination of iodophenyl esters as tool for the traceless staudinger ligation
Pretze, Marc,Flemming, Anke,Koeckerling, Martin,Mamata, Constantin
experimental part, p. 1128 - 1136 (2011/01/09)
A new synthetic pathway for the preparation of ω-functionalized 2-iodophenyl esters as starting materials for the synthesis of substituted phosphanes is described. A radiolabeling of these esters with fluorine-18 has led to building blocks which were reacted with HPPh2 in a Pd-catalyzed P-C cross coupling to establish new phosphanes. These compounds can be applied as mild and bioorthogonal radiolabeling agents by means of the traceless Staudinger ligation. A route to access this class of compounds has been established.
