20185-55-1Relevant articles and documents
Dilithium Amides as a Modular Bis-Anionic Ligand Platform for Iron-Catalyzed Cross-Coupling
Neate, Peter G.N.,Zhang, Bufan,Conforti, Jessica,Brennessel, William W.,Neidig, Michael L.
supporting information, p. 5958 - 5963 (2021/08/18)
Dilithium amides have been developed as a bespoke and general ligand for iron-catalyzed Kumada-Tamao-Corriu cross-coupling reactions, their design taking inspiration from previous mechanistic and structural studies. They allow for the cross-coupling of alkyl Grignard reagents with sp2-hybridized electrophiles as well as aryl Grignard reagents with sp3-hybridized electrophiles. This represents a rare example of a single iron-catalyzed system effective across diverse coupling reactions without significant modification of the catalytic protocol, as well as remaining operationally simple.
Enabling Metallophotoredox Catalysis in Parallel Solution-Phase Synthesis Using Disintegrating Reagent Tablets
Borlinghaus, Niginia,Sch?nfeld, Barbara,Heitz, Stephanie,Klee, Johanna,Vukeli?, Stella,Braje, Wilfried M.,Jolit, Anais
supporting information, p. 16535 - 16547 (2021/12/02)
Compressed tablets containing a mixture of a photocatalyst, a nickel catalyst, an inorganic base, and an inert excipient are employed as a fast, safe, and user-friendly chemical delivery system for two different metallophotoredox-catalyzed reactions. This delivery method simplifies the preparation of compound libraries using photoredox chemistry in a parallel setting. The reagent tablets were successfully applied to late-stage functionalization of drug-like intermediates. These tablets can be prepared with various reagents and catalysts in different sizes and be stored on the bench thanks to blister packaging.
Oxidative esterification of alcohols by a single-side organically decorated Anderson-type chrome-based catalyst
Wang, Jingjing,Jiang, Feng,Tao, Chaofu,Yu, Han,Ruhlmann, Laurent,Wei, Yongge
supporting information, p. 2652 - 2657 (2021/04/21)
The direct esterification of alcohols with non-noble metal-based catalytic systems faces great challenges. Here, we report a new chrome-based catalyst stabilized by a single pentaerythritol decorated Anderson-type polyoxometalate, [N(C4H9)4]3[CrMo6O18(OH)3C{(OCH2)3CH2OH}], which can realize the efficient transformation from alcohols to esters by H2O2oxidation in good yields and high selectivity without extra organic ligands. A variety of alcohols with different functionalities including some natural products and pharmaceutical intermediates are tolerated in this system. The chrome-based catalyst can be recycled several times and still keep the original configuration and catalytic activity. We also propose a reasonable catalytic mechanism and prove the potential for industrial applications.
Aerobic Oxidative Cleavage and Esterification of C(OH)–C Bonds
Liu, Mingyang,Zhang, Zhanrong,Yan, Jiang,Liu, Shuaishuai,Liu, Huizhen,Liu, Zhaotie,Wang, Weitao,He, Zhenhong,Han, Buxing
, p. 3288 - 3296 (2020/10/20)
C(OH)–C bonds are widely distributed in naturally renewable biomass, such as carbohydrates, lignin, and their platform molecules. Selective cleavage and functionalization of C(OH)–C bonds is an attractive strategy in terms of producing value-added chemicals from biomass. However, effective transformation of alcohols into esters by activation of C(OH)–C bonds has not been achieved so far. Herein, for the first time, we report selective cleavage and esterification of C(OH)–C bonds, catalyzed by inexpensive copper salts, using environmentally benign oxygen as the oxidant, to afford methyl esters in excellent yields. A diverse range of phenylethanol derivatives that contain C(OH)–C bonds were effectively converted into methyl benzoates. Detailed analysis revealed that the high efficiency and selectivity resulted mainly from the fact that, in addition to the major esterification reaction, the side products (e.g., olefins and acids) were also transformed in situ into esters in the reaction system. C(OH)–C bonds are widely distributed in naturally renewable biomass. In the context of developing future biorefineries, selective cleavage and functionalization of C(OH)–C bonds are crucial and represent an attractive strategy in terms of producing value-added chemical compounds from biomass resources. In the current manuscript, we report, for the first time, an effective and selective method for the cleavage and esterification of C(OH)–C bonds of alcohols to produce esters, by using environmentally benign O2 as the terminal oxidant and inexpensive commercially available copper salts as catalysts. Furthermore, a detailed mechanistic study revealed that, in addition to the major esterification route, side products (e.g., olefins and acids), which are inevitably generated under oxidative and basic conditions, were also simultaneously converted into esters, thus significantly improving the final yields of target ester products. Native lignin represents the only naturally sustainable aromatic resource. Transformation of native lignin into valuable aromatics would make a great contribution to our planet. We report, for the first time, the effective transformation of alcohols into esters by esterification of C(OH)–C bonds, which offers a new way for the simultaneous degradation and functionalization of lignin. This reaction promotes new explorations for biomass valorization.
Palladium-Catalyzed Chlorocarbonylation of Aryl (Pseudo)Halides Through In Situ Generation of Carbon Monoxide
Bismuto, Alessandro,Boehm, Philip,Morandi, Bill,Roediger, Sven
, p. 17887 - 17896 (2020/08/19)
An efficient palladium-catalyzed chlorocarbonylation of aryl (pseudo)halides that gives access to a wide range of carboxylic acid derivatives has been developed. The use of butyryl chloride as a combined CO and Cl source eludes the need for toxic, gaseous carbon monoxide, thus facilitating the synthesis of high-value products from readily available aryl (pseudo)halides. The combination of palladium(0), Xantphos, and an amine base is essential to promote this broadly applicable catalytic reaction. Overall, this reaction provides access to a great variety of carbonyl-containing products through in situ transformation of the generated aroyl chloride. Combined experimental and computational studies support a reaction mechanism involving in situ generation of CO.
Novel Class of Colony-Stimulating Factor 1 Receptor Kinase Inhibitors Based on an o-Aminopyridyl Alkynyl Scaffold as Potential Treatment for Inflammatory Disorders
Xie, Zhicheng,Wu, Bing,Liu, Yingqiang,Ren, Wenming,Tong, Linjiang,Xiang, Caigui,Wei, Aihuan,Gao, Yuanzhuo,Zeng, Limin,Xie, Hua,Tang, Wei,Hu, Youhong
, p. 1397 - 1414 (2020/02/04)
Colony-stimulating factor 1 receptor (CSF-1R) is involved in inflammatory disorders as well as in many types of cancer. Based on high-throughput screening and docking results, we performed a detailed structure-activity-relationship study, leading to the d
5-Phenyl-1,3,4-oxadiazol-2(3 H)-ones Are Potent Inhibitors of Notum Carboxylesterase Activity Identified by the Optimization of a Crystallographic Fragment Screening Hit
Mahy, William,Willis, Nicky J.,Zhao, Yuguang,Woodward, Hannah L.,Svensson, Fredrik,Sipthorp, James,Vecchia, Luca,Ruza, Reinis R.,Hillier, James,Kj?r, Svend,Frew, Sarah,Monaghan, Amy,Bictash, Magda,Salinas, Patricia C.,Whiting, Paul,Vincent, Jean-Paul,Jones, E. Yvonne,Fish, Paul V.
, p. 12942 - 12956 (2020/11/13)
Carboxylesterase Notum is a negative regulator of the Wnt signaling pathway. There is an emerging understanding of the role Notum plays in disease, supporting the need to discover new small-molecule inhibitors. A crystallographic X-ray fragment screen was performed, which identified fragment hit 1,2,3-Triazole 7 as an attractive starting point for a structure-based drug design hit-To-lead program. Optimization of 7 identified oxadiazol-2-one 23dd as a preferred example with properties consistent with drug-like chemical space. Screening 23dd in a cell-based TCF/LEF reporter gene assay restored the activation of Wnt signaling in the presence of Notum. Mouse pharmacokinetic studies with oral administration of 23dd demonstrated good plasma exposure and partial blood-brain barrier penetration. Significant progress was made in developing fragment hit 7 into lead 23dd (>600-fold increase in activity), making it suitable as a new chemical tool for exploring the role of Notum-mediated regulation of Wnt signaling.
Deoxygenative cross-electrophile coupling of benzyl chloroformates with aryl iodides
Pan, Yingying,Gong, Yuxin,Song, Yanhong,Tong, Weiqi,Gong, Hegui
, p. 4230 - 4233 (2019/05/06)
This work describes Ni-catalyzed cross-electrophile coupling of benzyl chloroformate derivatives with aryl iodides that generates a wide range of diaryl methane products. The mild reaction conditions merit the C-O bond radical fragmentation of benzyl chloroformates via halide abstraction or a single electron reduction by a Ni catalyst. This work offers a new substrate type for cross-electrophile couplings.
Aldehydes as potential acylating reagents for oxidative esterification by inorganic ligand-supported iron catalysis
Yu, Han,Wang, Jingjing,Wu, Zhikang,Zhao, Qixin,Dan, Demin,Han, Sheng,Tang, Jiangjiang,Wei, Yongge
supporting information, p. 4550 - 4554 (2019/08/21)
The oxidative esterification of various aldehydes with alcohols could be achieved by a heterogeneous iron(iii) catalyst supported on a ring-like POM inorganic ligand under mild conditions, affording the corresponding esters, including several drug molecules and natural products, in high yields. ESI-MS and control experiments demonstrated that POM-FeV(O) was the active catalytic species and the plausible mechanism was presented. More importantly, the 6th run of the iron catalyst recycles shows only a slight decrease in the yield.
Chloride-Induced Highly Active Au Catalyst for Methyl Esterification of Alcohols
Zhang, Chengming,Wang, Yongzhao
, p. 249 - 254 (2019/02/13)
Chloride is generally regarded as a harmful species for the heterogeneous catalysts, especially Au catalysts. In this work, a series of active Au/NiOx catalysts were successfully prepared with co-precipitation method by tracking the concentrations of chloride in the re-dispersed aqueous solutions. For methyl esterification of alcohols, the highest active Au/NiOx catalysts could be prepared from aqueous solutions containing 8-13 ppm chloride, the yield of methyl benzoate of catalyst Au/NiOx-9 was 99%. The catalyst structures and the role of chloride in catalysts were explored by ICP, BET, XPS, TEM and EXAFS characterizations. It was found that the appropriate amount of residual chloride in Au catalysts was beneficial to their catalytic activities. Especially for Au/NiOx-9, the appropriate amount of residual chloride had positive effects on the physicochemical properties of Au/NiOx catalyst, the position of Au nanoparticles (NPs) located on NiOx crystallites and the ratio of Auδ+/Au0 in catalyst, which together resulted in its high reactivity.
