610-97-9Relevant articles and documents
Connecting binuclear Pd(III) and mononuclear Pd(IV) chemistry by Pd-Pd bond cleavage
Powers, David C.,Lee, Eunsung,Ariafard, Alireza,Sanford, Melanie S.,Yates, Brian F.,Canty, Allan J.,Ritter, Tobias
, p. 12002 - 12009 (2012)
Oxidation of binuclear Pd(II) complexes with PhICl2 or PhI(OAc)2 has previously been shown to afford binuclear Pd(III) complexes featuring a Pd-Pd bond. In contrast, oxidation of binuclear Pd(II) complexes with electrophilic trifluoromethylating ("CF3 +") reagents has been reported to afford mononuclear Pd(IV) complexes. Herein, we report experimental and computational studies of the oxidation of a binuclear Pd(II) complex with "CF3 +" reagents. These studies suggest that a mononuclear Pd(IV) complex is generated by an oxidation-fragmentation sequence proceeding via fragmentation of an initially formed, formally binuclear Pd(III), intermediate. The observation that binuclear Pd(III) and mononuclear Pd(IV) complexes are accessible in the same reactions offers an opportunity for understanding the role of nuclearity in both oxidation and subsequent C-X bond-forming reactions.
Method for preparing iodo-benzoic acid (ester) by improving moral Michael reaction
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, (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%.
Pd/Cu-Catalyzed Vinylation of Terminal Alkynes with (2-Bromoethyl)diphenylsulfonium Triflate
Ming, Xiao-Xia,Wu, Shuai,Tian, Ze-Yu,Song, Jia-Wei,Zhang, Cheng-Pan
supporting information, p. 6795 - 6800 (2021/09/08)
The potential of (2-bromoethyl)diphenylsulfonium triflate to be a powerful vinylation reagent was determined by the Sonogashira cross-coupling reactions with terminal alkynes. The vinylation proceeded smoothly at 25 °C under Pd/Cu catalysis to afford a variety of 1- and 2-unsubstituted 1,3-enynes in moderate to excellent yields. This protocol represents the first application of (2-haloethyl)diphenylsulfonium triflate as a CH═CH2 transfer source in organic synthesis.
Mechanochemical-Cascaded C-N Cross-Coupling and Halogenation Using N-Bromo- And N-Chlorosuccinimide as Bifunctional Reagents
Bera, Shyamal Kanti,Mal, Prasenjit
, p. 14144 - 14159 (2021/09/13)
Exploration of alternative energy sources for chemical transformations has gained significant interest from chemists, and mechanochemistry is one of those sources. Herein, we report the use of N-bromosuccinimides (NBS) and N-chlorosuccinimides (NCS) as bifunctional reagents for a cascaded C-N bond formation and subsequent halogenation reactions. Under the solvent-free mechanochemical (ball-milling) conditions, the synthesis of a wide range of phenanthridinone derivatives from N-methoxy-[1,1′-biphenyl]-2-carboxamides is accomplished. During the reactions, NBS and NCS first assisted the oxidative C-N coupling reaction and subsequently promoted a halogenation reaction. Thus, the role of NBS and NCS was established to be bifunctional. Overall, a mild, solvent-free, convenient, one-pot, and direct synthesis of various bromo- and chloro-substituted phenanthridinone derivatives was achieved.
Transition-Metal-Free Synthesis of Phenanthridinones through Visible-Light-Driven Oxidative C–H Amidation
Usami, Kaoru,Yamaguchi, Eiji,Tada, Norihiro,Itoh, Akichika
, p. 1496 - 1504 (2019/06/27)
The treatment of N-aryl biphenylcarboxamide, 1-chloroanthraquinone (1-Cl-AQN) catalyst, and K2CO3 in CHCl3 under visible light irradiation affords phenanthridinone via radical cyclization. This reaction proceeds under transition-metal-free condition, room temperature, and direct C–H amidation. Mechanistic studies indicate that amidyl radical generation proceeds by visible light induced proton coupled electron transfer (PCET) from N–H bond of the amide.
Development of Novel N-hydroxypyridone Derivatives as Potential Anti-Ischemic Stroke Agents
Hu, Linghao,Feng, Hongxuan,Zhang, Hongguang,Yu, Songda,Zhao, Qinyuan,Wang, Wei,Bao, Fengxia,Ding, Xun,Hu, Jiajing,Wang, Manjiong,Xu, Yixiang,Wu, Zengrui,Li, Xiaokang,Tang, Yun,Mao, Fei,Chen, Xiaoyan,Zhang, Haiyan,Li, Jian
supporting information, p. 1051 - 1067 (2020/03/10)
Our previous study had identified ciclopirox (CPX) as a promising lead compound for treatment of ischemic stroke. To find better neuroprotective agents, a series of N-hydroxypyridone derivatives based on CPX were designed, synthesized, and evaluated in this study. Among these derivatives, compound 11 exhibits significant neuroprotection against oxygen glucose deprivation and oxidative stress-induced injuries in neuronal cells. Moreover, compound 11 possesses good blood-brain barrier permeability and superior antioxidant capability. In addition, a complex of compound 11 with olamine-11·Ola possesses good water solubility, negligible hERG inhibition, and superior metabolic stability. The in vivo experiment demonstrates that 11·Ola significantly reduces brain infarction and alleviates neurological deficits in middle cerebral artery occlusion rats. Hence, compound 11·Ola is identified in our research as a prospective prototype in the innovation of stroke treatment.
Lipshutz-type bis(amido)argentates for directed: Ortho argentation
Tezuka, Noriyuki,Hirano, Keiichi,Peel, Andrew J.,Wheatley, Andrew E. H.,Miyamoto, Kazunori,Uchiyama, Masanobu
, p. 1855 - 1861 (2020/03/03)
Bis(amido)argentate (TMP)2Ag(CN)Li2 (3, TMP-Ag-ate; TMP = 2,2,6,6-tetramethylpiperidido) was designed as a tool for chemoselective aromatic functionalization via unprecedented directed ortho argentation (DoAg). X-Ray crystallographic analysis showed that 3 takes a structure analogous to that of the corresponding Lipshutz cuprate. DoAg with this TMP-Ag-ate afforded multifunctional aromatics in high yields in processes that exhibited high chemoselectivity and compatibility with a wide range of functional groups. These included organometallics- A nd transition metal-susceptible substituents such as methyl ester, aldehyde, vinyl, iodo, (trifluoromethanesulfonyl)oxy and nitro groups. The arylargentates displayed good reactivity with various electrophiles. Chalcogen (S, Se, and Te) installation and azo coupling reactions also proceeded efficiently.
Reconciling Electrostatic and n→π* Orbital Contributions in Carbonyl Interactions
Adam, Catherine,Borsley, Stefan,Cockroft, Scott L.,Ling, Kenneth B.,Mati, Ioulia K.,Muchowska, Kamila B.,Nichol, Gary S.,Pascoe, Dominic J.,Smolyar, Ivan V.
supporting information, p. 14602 - 14608 (2020/07/06)
Interactions between carbonyl groups are prevalent in protein structures. Earlier investigations identified dominant electrostatic dipolar interactions, while others implicated lone pair n→π* orbital delocalisation. Here these observations are reconciled.
Generation of Organozinc Reagents by Nickel Diazadiene Complex Catalyzed Zinc Insertion into Aryl Sulfonates
Klein, Philippe,Lechner, Vivien Denise,Schimmel, Tanja,Hintermann, Lukas
supporting information, p. 176 - 180 (2019/12/11)
The generation of arylzinc reagents (ArZnX) by direct insertion of zinc into the C?X bond of ArX electrophiles has typically been restricted to iodides and bromides. The insertions of zinc dust into the C?O bonds of various aryl sulfonates (tosylates, mesylates, triflates, sulfamates), or into the C?X bonds of other moderate electrophiles (X=Cl, SMe) are catalyzed by a simple NiCl2–1,4-diazadiene catalyst system, in which 1,4-diazadiene (DAD) stands for diacetyl diimines, phenanthroline, bipyridine and related ligands. Catalytic zincation in DMF or NMP solution at room temperature now provides arylzinc sulfonates, which undergo typical catalytic cross-coupling or electrophilic substitution reactions.
Synthesis of 5H-Selenopheno[3,2-c]isochromen-5-ones Promoted by Dialkyl Diselenides and Oxone
Goulart, Helen A.,Neto, José S. S.,Barcellos, Angelita M.,Barcellos, Thiago,Silva, Márcio S.,Alves, Diego,Jacob, Raquel G.,Lenard?o, Eder J.,Perin, Gelson
supporting information, p. 3403 - 3411 (2019/05/28)
We describe here for the first time the synthesis of isochromenones fused to selenophenes. 5H-Selenopheno[3,2-c]isochromen-5-ones were obtained through a double intramolecular cyclization of methyl 2-(organyl-1,3-diynyl)benzoate promoted by electrophilic species of selenium generated in situ by the reaction of dialkyl diselenides with Oxone, using ethanol as solvent. The reactions were conducted satisfactorily under mild conditions, using a range of 1,3-diynes and dialkyl diselenides as substrates. A total of sixteen unprecedent 5H-selenopheno[3,2-c]isochromen-5-ones were selectively obtained in moderate to good yields (40–86%) under reflux in an open flask and in short reaction times (1.0–2.5 h). (Figure presented.).
