42181-97-5Relevant academic research and scientific papers
A Modular Synthesis of Modified Phosphoanhydrides
Hofer, Alexandre,Cremosnik, Gregor S.,Müller, Andr C.,Giambruno, Roberto,Trefzer, Claudia,Superti-Furga, Giulio,Bennett, Keiryn L.,Jessen, Henning J.
, p. 10116 - 10122 (2015)
Phosphoanhydrides (P-anhydrides) are ubiquitously occurring modifications in nature. Nucleotides and their conjugates, for example, are among the most important building blocks and signaling molecules in cell biology. To study and manipulate their biological functions, a diverse range of analogues have been developed. Phosphate-modified analogues have been successfully applied to study proteins that depend on these abundant cellular building blocks, but very often both the preparation and purification of these molecules are challenging. This study discloses a general access to P-anhydrides, including different nucleotide probes, that greatly facilitates their preparation and isolation. The convenient and scalable synthesis of, for example, 18O labeled nucleoside triphosphates holds promise for future applications in phosphoproteomics. Building the building blocks: This study discloses a general method for the functionalization of unprotected nucleotides and sugar phosphates with P-amidites in a highly modular way. The strategy facilitates the preparation of thiophosphate-containing nucleotides, 18O-labeled nucleoside triphosphates, and farnesylated nucleotides, as well as a range of dinucleoside polyphosphates and nucleotide sugars.
Silver/Palladium Relay Catalyzed Cross-Coupling of N'-Acetyl-8-quinolinesulfonylhydrazide with Alcohols: An Easy Access to 8-Quinolinesulfinate Esters
Yadav, Anamika,Ambule, Mayur D.,Kant, Ruchir,Srivastava, Ajay K.
, p. 5709 - 5713 (2020)
An efficient strategy for the synthesis of unexplored 8-quinolinesulfinate esters has been reported. The method involves in situ generation of quinoline sulfinate from N'-acetylquinoline-8-sulfonohydrazide via silver mediated cleavage followed by palladium-catalyzed cross-coupling with 1° and 2° alcohols to yield sulfinate esters. A variety of substituted alcohols were successfully employed in the reaction. Control experiments performed to understand the mechanism, revealed that the transformation follows a radical pathway and the alcohol oxygen get incorporated in the resulting sulfinate esters. Two of the chirally pure alcohols were also used in the transformation to study the diastereoselectivity in the reaction. In order to demonstrate the synthetic utility, a representative allyl-quinoline-8-sulfinate 3f was successfully converted into the 8-(allylsulfonyl)-quinoline 4 via palladium(II) acetate mediated isomerization.
Copper-catalyzed oxidative cleavage of Passerini and Ugi adducts in basic medium yielding α-ketoamides
Ghoshal, Anirban,Ambule, Mayur D.,Sravanthi, Revoju,Taneja, Mohit,Srivastava, Ajay Kumar
supporting information, p. 14459 - 14474 (2019/10/01)
The aerobic oxidative cleavage of Passerini and Ugi adducts in the presence of base and copper(i) iodide is studied in detail. The oxidative cleavage yields α-ketoamides along with acids and amides from Passerini and Ugi adducts respectively. Mechanistic investigations revealed that the reaction proceeds via a radical pathway involving molecular oxygen. Control experiments with 18O-labeled Passerini adducts confirmed that molecular oxygen is the source of oxygen in α-ketoamides. A variety of Passerini and Ugi adducts were studied to explore the effect of substitution. Overall, the present study provides an insight into the reactivity of Passerini and Ugi adducts in strong basic conditions along with a method to prepare α-ketoamides.
Catalytic Tandem Friedel-Crafts Alkylation/C4-C3 Ring-Contraction Reaction: An Efficient Route for the Synthesis of Indolyl Cyclopropanecarbaldehydes and Ketones
Turnu, Francesca,Luridiana, Alberto,Cocco, Andrea,Porcu, Stefania,Frongia, Angelo,Sarais, Giorgia,Secci, Francesco
supporting information, p. 7329 - 7332 (2019/10/02)
A general strategy for the synthesis of indolyl cyclopropanecarbaldehydes and ketones via a Br?nsted acid-catalyzed indole nucleophilic addition/ring-contraction reaction sequence has been exploited. The procedure leads to a wide panel of cyclopropyl carbonyl compounds in generally high yields with a broad substrate scope.
DMSO-Triggered Complete Oxygen Transfer Leading to Accelerated Aqueous Hydrolysis of Organohalides under Mild Conditions
Liu, Haicheng,Liu, Jianping,Cheng, Xiaokai,Jia, Xiaojuan,Yu, Lei,Xu, Qing
, p. 2994 - 2998 (2019/01/04)
Addition of DMSO is found to greatly accelerate the aqueous hydrolysis of organohalides to alcohols, providing a neutral, more efficient, milder and more economic process. Mechanistic studies using 18O-DMSO and 18O-H2O showed that, contrary to the opinion that DMSO works as a dipolar solvent to enhance water's nucleophilicity, the accelerating effect comes from a complete oxygen transfer from DMSO to organohalides through generation of ROS+Me2?X? salts through C?O bond formation, followed by O?S bond disassociative hydrolysis of ROS+Me2?X? with water. This method is applicable to a wide range of organohalides and thus may have potential for practical industrial application, owing to easy recovery of DMSO from the H2O/DMSO mixture by regular vacuum rectification.
Acid-catalyzed synthesis of functionalized arylthio cyclopropane carbaldehydes and ketones
Porcu, Stefania,Luridiana, Alberto,Martis, Alberto,Frongia, Angelo,Sarais, Giorgia,Aitken, David J.,Boddaert, Thomas,Guillot, Regis,Secci, Francesco
supporting information, p. 13547 - 13550 (2019/01/06)
A general strategy for the synthesis of arylthio cyclopropyl carbaldehydes and ketones via a Br?nsted acid catalyzed arylthiol addition/ring contraction reaction sequence has been exploited. The procedure led to a wide panel of cyclopropyl carbaldehydes in generally high yields and with broad substrate scope. Mechanistic aspects and synthetic applications of this procedure were investigated.
Gold(I)-catalyzed synthesis of unsymmetrical ethers using alcohols as alkylating reagents
Liu, Yongxiang,Wang, Xiaoyu,Wang, Yanshi,Du, Chuan,Shi, Hui,Jin, Shengfei,Jiang, Chongguo,Xiao, Jianyong,Cheng, Maosheng
, p. 1029 - 1036 (2015/03/30)
A microwave-irradiated alcohol-protecting strategy based on gold catalysis utilizing benzyl alcohol, tert-butyl alcohol and triphenylmethanol as alkylating reagents has been developed. This protecting strategy has wide functional group tolerance with satisfactory yields for the majority of the selected alcohols. The mechanism of this transformation was probed with oxygen-18 isotope labelled alcohols assisted by GC-MS techniques and chemical kinetic experiments. This strategy provides an efficient, straightforward and alternative approach to the preparation of benzyl, tert-butyl and trityl ethers in organic synthesis.
Photocatalytic oxidation of benzyl alcohol by homogeneous CuCl2/solvent: A model system to explore the role of molecular oxygen
Meng, Chao,Yang, Kai,Fu, Xianzhi,Yuan, Rusheng
, p. 3760 - 3766 (2015/06/16)
The oxidation of alcohols to the corresponding carbonyl compounds is a pivotal reaction in organic synthesis. Under visible light irradiation, the homogeneous CuCl2 and cheap solvent oxidized benzyl alcohol into benzaldehyde with a selectivity higher than 95% using molecular oxygen as an oxidant. The formation of a visible light responsive complex between Cu(II) and solvent is responsible for the occurrence of the oxidation of benzyl alcohol. During the photocatalytic process, molecular oxygen was not incorporated into the final benzaldehyde and only involved in the oxidation of Cu(I) into Cu(II) in which it served as a terminal hydrogen acceptor to form H2O. A similar role of molecular oxygen has also been observed in the heterogeneous TiO2 photocatalytic system. The understanding of the role of molecular oxygen helps us to further design new classes of synthetic organic reactions by photocatalytic processes.
Reactivity of an iron-oxygen oxidant generated upon oxidative decarboxylation of biomimetic iron(II) α-hydroxy acid complexes
Paria, Sayantan,Chatterjee, Sayanti,Paine, Tapan Kanti
, p. 2810 - 2821 (2014/04/03)
Three biomimetic iron(II) α-hydroxy acid complexes, [(Tp Ph2)FeII(mandelate)(H2O)] (1), [(Tp Ph2)FeII(benzilate)] (2), and [(TpPh2)Fe II(HMP)] (3), together with two iron(II) α-methoxy acid complexes, [(TpPh2)FeII(MPA)] (4) and [(Tp Ph2)FeII(MMP)] (5) (where HMP = 2-hydroxy-2- methylpropanoate, MPA = 2-methoxy-2-phenylacetate, and MMP = 2-methoxy-2-methylpropanoate), of a facial tridentate ligand TpPh2 [where TpPh2 = hydrotris(3,5-diphenylpyrazole-1-yl)borate] were isolated and characterized to study the mechanism of dioxygen activation at the iron(II) centers. Single-crystal X-ray structural analyses of 1, 2, and 5 were performed to assess the binding mode of an α-hydroxy/methoxy acid anion to the iron(II) center. While the iron(II) α-methoxy acid complexes are unreactive toward dioxygen, the iron(II) α-hydroxy acid complexes undergo oxidative decarboxylation, implying the importance of the hydroxyl group in the activation of dioxygen. In the reaction with dioxygen, the iron(II) α-hydroxy acid complexes form iron(III) phenolate complexes of a modified ligand (TpPh2*), where the ortho position of one of the phenyl rings of TpPh2 gets hydroxylated. The iron(II) mandelate complex (1), upon decarboxylation of mandelate, affords a mixture of benzaldehyde (67%), benzoic acid (20%), and benzyl alcohol (10%). On the other hand, complexes 2 and 3 react with dioxygen to form benzophenone and acetone, respectively. The intramolecular ligand hydroxylation gets inhibited in the presence of external intercepting agents. Reactions of 1 and 2 with dioxygen in the presence of an excess amount of alkenes result in the formation of the corresponding cis-diols in good yield. The incorporation of both oxygen atoms of dioxygen into the diol products is confirmed by 18O-labeling studies. On the basis of reactivity and mechanistic studies, the generation of a nucleophilic iron-oxygen intermediate upon decarboxylation of the coordinated α-hydroxy acids is proposed as the active oxidant. The novel iron-oxygen intermediate oxidizes various substrates like sulfide, fluorene, toluene, ethylbenzene, and benzaldehyde. The oxidant oxidizes benzaldehyde to benzoic acid and also participates in the Cannizzaro reaction.
AlCl3-catalyzed oxidation of alcohol
Wu, Shang,Ma, Hengchang,Lei, Ziqiang
experimental part, p. 8641 - 8647 (2010/11/19)
The metalloid salt AlCl3, applied as catalyst for the oxidation of alcohol was presented. In water media, variety of alcohols, including inactive aliphatic alcohols, could be converted into corresponding carbonyl compounds with excellent conversion and selectivity. Especially, this green reaction system also exemplifies advances toward the domino synthesis alkenes in good yields (>52%) and perfect purity (>99%), and the reaction gave preferentially the E-isomer. The obvious advantages of the present protocol include green reaction media, wide functional group tolerance, convenient product isolation, as well as grams reaction scale.
