- Electrochemical oxidation-induced benzyl C–H carbonylation for the synthesis of aromatic α-diketones
-
Electrochemical oxidation-induced direct carbonylation of benzyl C–H bond for the synthesis of aromatic α-diketones is described. In this process, tetrabutylammonium iodide (nBu4NI) not only acts as an electrolyte, but its iodine anion is oxidized to an iodine radical at the anode, acting as a hydrogen atom transfer agent. The iodine radical extracts the benzyl hydrogen atom and causes the carbonylation of the benzyl position, where O2 in the air is used as an oxygen source.
- Tan, Yu-Fang,Chen, Yuan,Li, Rui-Xue,Guan, Zhi,He, Yan-Hong
-
supporting information
(2021/12/21)
-
- Rhodium-Catalyzed Aerobic Decomposition of 1,3-Diaryl-2-diazo-1,3-diketones: Mechanistic Investigation and Application to the Synthesis of Benzils
-
The conversion of 1,3-diaryl-2-diazo-1,3-diketones to 1,2-daryl-1,2-diketones (benzils) is reported based on a rhodium(II)-catalyzed aerobic decomposition process. The reaction occurs at ambient temperatures and can be catalyzed by a few dirhodium carboxylates (5 mol %) under a balloon pressure of oxygen. Moreover, an oxygen atom from the O2 reagent is shown to be incorporated into the product, and this is accompanied by the extrusion of a carbonyl unit from the starting materials. Mechanistically, it is proposed that the decomposition may proceed via the interaction of a ketene intermediate resulting from a Wolff rearrangement of the carbenoid, with a rhodium peroxide or peroxy radical species generated upon the activation of molecular oxygen. The proposed mechanism has been supported by the results from a set of controlled experiments. By using this newly developed strategy, a large array of benzil derivatives as well as 9,10-phenanthrenequinone were synthesized from the corresponding diazo substrates in varying yields. On the other hand, the method did not allow the generation of benzocyclobutene-1,2-dione from 2-diazo-1,3-indandione because of the difficulty of inducing the initial rearrangement.
- Zhu, Jia-Liang,Tsai, Yi-Ting
-
p. 813 - 828
(2020/12/22)
-
- Synthesis of 1,2-diketones by mercury-catalyzed alkyne oxidation
-
The first mercury-catalyzed synthesis of 1,2-diketones by alkyne oxidation has been developed. This inexpensive method extends the potential of mercury catalysis and allows the rapid construction of various 1,2-diketones and α-carbonyl amides in good yields with high functional group tolerance.
- Mei, Xiaochuan,Hu, Weican,Gao, Kexin,Gao, Haotian,Wang, Chaoyang,Qian, Guoying,Rong, Zhouting
-
supporting information
p. 2661 - 2667
(2021/07/09)
-
- Catalyst-Free and Transition-Metal-Free Approach to 1,2-Diketones via Aerobic Alkyne Oxidation
-
A catalyst-free and transition-metal-free method for the synthesis of 1,2-diketones from aerobic alkyne oxidation was reported. The oxidation of various internal alkynes, especially more challenging aryl-alkyl acetylenes, proceeded smoothly with inexpensive, easily handled, and commercially available potassium persulfate and an ambient air balloon, achieving the corresponding 1,2-diketones with up to 85% yields. Meanwhile, mechanistic studies indicated a radical process, and the two oxygen atoms in the 1,2-diketons were most likely from persulfate salts and molecular oxygen, respectively, rather than water.
- Shen, Duyi,Wang, Hongyan,Zheng, Yanan,Zhu, Xinjing,Gong, Peiwei,Wang, Bin,You, Jinmao,Zhao, Yulei,Chao, Mianran
-
p. 5354 - 5361
(2021/05/05)
-
- Lanthanide complexes based on an anthraquinone derivative ligand and applications as photocatalysts for visible-light driving photooxidation reactions
-
Four isostructural lanthanide coordination complexes based on 3,7-diamino-9,10-anthraquinone-2,6-disulfonate (dianionic, L) have been synthesized by hydrothermal method, namely [Er(L)(H2O)6]?[Er(H2O)8]?2L?8H2O (Er-L), [Tm(L)(H2O)6]?[Tm(H2O)8]?2L?8.5H2O (Tm-L), [Yb(L)(H2O)6]?[Yb(H2O)8]?2L?9H2O (Yb-L), [Lu(L)(H2O)6]?[Lu(H2O)8]?2L?9H2O (Lu-L). Single-crystal X-ray analysis reveals the existence of both coordinated and free ligand L in the crystal structure. Versatile sulfonate groups on these distinct L ligands, together with very rich coordinated and lattice water molecules, form a lot of hydrogen-bonding motifs that contribute to the stabilization of the crystal packing. It is interesting that the ligands stack into columns through strong π-π interactions and the centroid-centroid distances are between 3.281 and 3.331 ?. These ligands are stacked in an alternate off-set mode to avoid the steric hindrance between the bulky sulfonate groups, generating a repeated structural unit involving six stacked ligands. These lanthanide complexes proved to be good heterogeneous photocatalyst for promoting the visible-light driving photooxidation reactions of diarylacetylenes and thioethers. The Er-L complex exhibited the best catalytic activity and showed good catalytic efficiency over a wide range of substrates for both reaction systems. The Er-L photocatalyst can be easily isolated by simple filtration as crystalline material upon completion of the photooxidation reaction without structure change, and can be recycled for at least five catalytic cycles with persistent catalytic efficiency without any need of activation or regeneration. This family of lanthanide complexes represent a category of promising heterogeneous photocatalysts in terms of green chemistry, with the potential of promoting organic transformations highly efficiently under the irradiation of visible light.
- Zhu, Ting-Ting,Tao, Yu-Tong,Sun, Yue,Wang, Xue,Zhang, Xiao-Wen,Chai, Jia-Lu,Han, Jie,Zhao, Xiao-Li,Chen, Xu-Dong
-
-
- Structural insights into the desymmetrization of bulky 1,2-dicarbonyls through enzymatic monoreduction
-
Benzil reductases are dehydrogenases preferentially active on aromatic 1,2-diketones, but the reasons for this peculiar substrate recognition have not yet been clarified. The benzil reductase (KRED1-Pglu) from the non-conventional yeast Pichia glucozyma showed excellent activity and stereoselectivity in the monoreduction of space-demanding aromatic 1,2-dicarbonyls, making this enzyme attractive as biocatalyst in organic chemistry. Structural insights into the stereoselective monoreduction of 1,2-diketones catalyzed by KRED1-Pglu were investigated starting from its 1.77 ? resolution crystal structure, followed by QM and classical calculations; this study allowed for the identification and characterization of the KRED1-Pglu reactive site. Once identified the recognition elements involved in the stereoselective desymmetrization of bulky 1,2-dicarbonyls mediated by KRED1-Pglu, a mechanism was proposed together with an in silico prediction of substrates reactivity.
- Rabuffetti, Marco,Cannazza, Pietro,Contente, Martina Letizia,Pinto, Andrea,Romano, Diego,Hoyos, Pilar,Alcantara, Andres R.,Eberini, Ivano,Laurenzi, Tommaso,Gourlay, Louise,Di Pisa, Flavio,Molinari, Francesco
-
supporting information
(2021/01/25)
-
- Aerobic oxygenation of α-methylene ketones under visible-light catalysed by a CeNi3complex with a macrocyclic tris(salen)-ligand
-
A hetero-tetranuclear CeNi3 complex with a macrocyclic ligand catalysed the aerobic oxygenation of a methylene group adjacent to a carbonyl group under visible-light radiation to produce the corresponding α-diketones. The visible-light induced homolysis of the Ce-O bond of a bis(enolate) intermediate is proposed prior to aerobic oxygenation.
- Fujiwara, Sakiko,Kon, Yoshihiro,Mashima, Kazushi,Nagae, Haruki,Okuda, Jun,Sakamoto, Kazutaka,Sato, Kazuhiko,Schindler, Tobias
-
supporting information
p. 11169 - 11172
(2021/11/04)
-
- Visible-Light-Induced Photocatalytic Oxidative Decarboxylation of Cinnamic Acids to 1,2-Diketones
-
A concerted metallophotoredox catalysis has been realized for the efficient decarboxylative functionalization of α,β-unsaturated carboxylic acids with aryl iodides in the presence of perylene bisimide dye to afford 1,2-diketones.
- Chand, Shiv,Pandey, Anand Kumar,Singh, Rahul,Singh, Krishna Nand
-
p. 6486 - 6493
(2021/05/06)
-
- One-pot cascade synthesis of α-diketones from aldehydes and ketones in water by using a bifunctional iron nanocomposite catalyst
-
A new methodology for the synthesis of α-diketones was reportedviaa one-pot cascade process from aldehydes and ketones catalyzed by a bifunctional iron nanocomposite using H2O2as a green oxidant in water. The one-pot strategy showed excellent catalytic stability, comprehensive suitability of substrates and important practical utility for directly synthesizing biologically active and medicinally valuable N-heterocyclesviaan intermittent process.
- Song, Tao,Zhou, Xin,Wang, Xiaoxue,Xiao, Jianliang,Yang, Yong
-
supporting information
p. 1955 - 1959
(2021/03/26)
-
- 1-butyl-3-methylimidazol-2-ylidene as an efficient catalyst for cross-coupling between aromatic aldehydes and N-aroylbenzotriazoles
-
Cross-coupling of aromatic aldehydes with N-aroylbenzotriazoles in [Bmim]Br in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) provided an efficient procedure for the synthesis of 1,2-diarylethane-1,2-diones.
- Phungpis, Baramee,Hahnvajanawong, Viwat
-
p. 651 - 657
(2021/02/27)
-
- Conversion of alkynes into 1,2-diketones using HFIP as sacrificial hydrogen donor and DMSO as dihydroxylating agent
-
A metal-free and hypervalent iodine free conversion of internal alkynes into 1,2-diketo compounds has been described. The efficacy of the present protocol rely on the use of HFIP (1,1,1,3,3,3-Hexafluoro-2-propanol) as reducing agent of alkynes and DMSO as dihydroxylating agent of olefins to acquire the desired chemical transformations. The obtained 1,2-diketones were further transformed into useful derivatives.
- Gujjarappa, Raghuram,Vodnala, Nagaraju,Putta,Ganga Reddy, Velma,Malakar, Chandi C.
-
supporting information
(2020/01/21)
-
- Visible light-induced aerobic oxidation of diarylalkynes to α-diketones catalyzed by copper-superoxo at room temperature
-
We have developed the visible light induced simple copper(ii) chloride catalyzed oxidation of diarylacetylenes to α-diketones by molecular oxygen at room temperature. The in situ generated copper(ii)-superoxo complex is a light-absorbing species that oxidizes inert diarylacetylenes to α-diketones. In contrast to reported photochemical processes, the current oxidation protocol does not require any exogenous photocatalyst or radical initiator. The green chemistry metrics evaluation signifies that the E-factor for the current oxidation process is ～2.3 times better than that of reported photochemical processes. The current reaction scores 63 on the EcoScale of 0-100, indicating an adequate synthesis process. Thus, the overall oxidation process is simple, environmentally benign, and economically feasible. This journal is
- Charpe, Vaibhav Pramod,Hwang, Kuo Chu,Sagadevan, Arunachalam
-
supporting information
p. 4426 - 4432
(2020/08/10)
-
- Dimethyl Sulfoxide as an Oxygen Atom Source Enabled Tandem Conversion of 2-Alkynyl Carbonyls to 1,2-Dicarbonyls
-
A tandem transformation of 2-alkynyl carbonyl compounds by means of a CuBr2/I2/DMSO/water system is developed, enabling the fromation of various functionalized 1,2-dicarbonyl compounds, including 1,2-diketones, α-keto amides and α-keto ester. This Cu-promoted iodine-mediated tandem procedure employs DMSO as the oxygen atom source of the formed carbonyl group through iodonium ion formation, nucleophilic DMSO addition and C?C bond cleavage cascades. (Figure presented.).
- Hu, Ming,Li, Jin-Heng,Li, Yang,Lu, Yuan,Luo, Mu-Jia
-
supporting information
(2020/05/01)
-
- Palladium-Catalyzed Oxidative C≡C Triple Bond Cleavage of 2-Alkynyl Carbonyl Compounds Toward 1,2-Dicarbonyl Compounds?
-
A new, general palladium-catalyzed oxidative strategy for the cleavage of the C≡C triple bond is presented. By employing PdCl2, CuBr2, TEMPO and air as the catalytic system and H2O as the carbonyl oxygen atom source, a wide range of 2-alkynyl carbonyl compounds, including 1,3-disubstituted prop-2-yn-1-ones, propiolamides and propiolates, lost an alkynyl carbon to access various 1,2-dicarbonyl compounds, e.g., 1,2-diones, 2-keto amides and 2-keto esters, through Wacker oxidation, intramolecular cyclization and C—C bond cleavage cascades.
- Hu, Ming,Li, Jin-Heng,Luo, Mu-Jia,Zhou, Ming-Bo
-
p. 553 - 558
(2020/04/20)
-
- Copper/Iodine-Cocatalyzed C-C Cleavage of 1,3-Dicarbonyl Compounds Toward 1,2-Dicarbonyl Compounds
-
A new, general oxidative route to transformations of 1,3-dicarbonyl compounds to 1,2-dicarbonyl compounds by merging copper and I2 catalysis is described. This method is applicable to broad 1,3-dicarbonyl compounds, including 1,3-diketones, 1,3-keto esters and 1,3-keto amides. Mechanistical studies show that the reaction is achieved via the C–C bond cleavage and CO release cascades.
- Chen, Li-Sha,Zhang, Lu-Bing,Tian, Yue,Li, Jin-Heng,Liu, Yong-Quan
-
supporting information
p. 5523 - 5526
(2020/09/02)
-
- A Bifunctional Iron Nanocomposite Catalyst for Efficient Oxidation of Alkenes to Ketones and 1,2-Diketones
-
We herein report the fabrication of a bifunctional iron nanocomposite catalyst, in which two catalytically active sites of Fe-Nx and Fe phosphate, as oxidation and Lewis acid sites, were simultaneously integrated into a hierarchical N,P-dual doped porous carbon. As a bifunctional catalyst, it exhibited high efficiency for direct oxidative cleavage of alkenes into ketones or their oxidation into 1,2-diketones with a broad substrate scope and high functional group tolerance using TBHP as the oxidant in water under mild reaction conditions. Furthermore, it could be easily recovered for successive recycling without appreciable loss of activity. Mechanistic studies disclose that the direct oxidation of alkenes proceeds via the formation of an epoxide as intermediate followed by either acid-catalyzed Meinwald rearrangement to give ketones with one carbon shorter or nucleophilic ring-opening to generate 1,2-diketones in a cascade manner. This study not only opens up a fancy pathway in the rational design of Fe-N-C catalysts but also offers a simple and efficient method for accessing industrially important ketones and 1,2-diketones from alkenes in a cost-effective and environmentally benign fashion.
- Ma, Zhiming,Ren, Peng,Song, Tao,Xiao, Jianliang,Yang, Yong,Yuan, Youzhu
-
p. 4617 - 4629
(2020/05/19)
-
- Ruthenium/dendrimer complex immobilized on silica-functionalized magnetite nanoparticles catalyzed oxidation of stilbenes to benzil derivatives at room temperature
-
A new ruthenium/dendrimer complex stabilized on the surface of silica-functionalized nano-magnetite was fabricated and well characterized. The nano-catalyst showed good activity in the synthesis of benzil derivatives via the oxidation of stilbenes with high turnover frequency (TOF) at room temperature. Moreover, the catalyst could also be reused up to fifteen times without any loss of its activity.
- Ghanaatzadeh, Niloofar,Hashemi, Hajar,Moghadam, Majid,Niknam, Khodabakhsh,Saberi, Dariush
-
-
- ICl/AgNO3 Co-catalyzed radical oxidation of diaryl- A nd alkylarylalkynes into 1,2-diketones
-
A novel ICl/AgNO3 co-catalyzed radical oxidation of diaryl- A nd alkylarylalkynes into 1,2-diketones is reported. The reaction proceeded smoothly under mild conditions and generated 1,2-diketones in moderate to good yields with a good tolerance of functional groups. Furthermore, the obtained C4-(1,2-diketoaryl)isoxazoles could react smoothly with 1,2-diaminobenzene to form C4-(3-arylquinoxalin-2-yl)isoxazoles. At last, a new one-pot strategy for the synthesis of quinoxalines from 1,2-diphenylethynes and 1,2-diaminobenzene is also reported.
- Yang, Wen,Chen, Yu,Yao, Yongqi,Yang, Xin,Lin, Qifu,Yang, Dingqiao
-
p. 11080 - 11090
(2019/09/09)
-
- Method for synthesizing 1,2-dicarbonyl compounds
-
The present invention provides a method for synthesizing 1,2-dicarbonyl compounds represented by a formula (II). The method comprises the steps of taking a substituted diphenylacetylene compound represented by a formula (I) as an initial substance, in the presence of an additive, an oxidizing agent and a solvent, conducting a reaction at a temperature of 0-50 DEG C, and conducting post-treatment to obtain a 1,2-dicarbonyl compound represented by the formula (II), wherein the additive is p-toluenesulfonic acid or phenylsulfonic acid. The synthetic method of the invention has the characteristicsof small environmental hazard, mild reaction conditions and simple operation.
- -
-
Paragraph 0054-0065
(2019/03/26)
-
- Substituent Effect in the Synthesis of α,α-Dibromoketones, 1,2-Dibromalkenes, and 1,2-Diketones from the Reaction of Alkynes and Dibromoisocyanuric Acid
-
Internal alkynes reacted with dibromoisocyanuric acid/H2O to afford α,α-dibromoketone and 1,2-diketone derivatives. Diarylalkynes with activating groups provided 1,2-diketone derivatives as the major products, whereas diarylalkynes with a non-activating group or alkylarylalkynes gave α,α-dibromoketone derivatives as the major products. In addition, diarylalkynes with deactivating groups provided 1,2-dibromoalkenes. The reaction was conducted at room temperature and showed good yields in most cases. Reaction pathways have been proposed on the basis of experimental observations and density functional theory (DFT) calculations. (Figure presented.).
- Cho, Eunjeong,Jayaraman, Aravindan,Lee, Junseong,Ko, Kyoung Chul,Lee, Sunwoo
-
p. 1846 - 1858
(2019/03/07)
-
- B2pin2-mediated copper-catalyzed oxidation of alkynes into 1,2-diketones using molecular oxygen
-
An intriguing aerobic oxidation of alkynes through copper catalysis is described, in which bis(pinacolato)diboron (B2pin2) played a dominant intermediary role in the formation 1,2-diketones. This novel protocol, which can be performed at room temperature, is versatile for various substituted alkynes, including diarylalkynes and arylalkylalkynes. The mechanism of this reaction was preliminarily investigated by control experiments.
- Zhai, Yadong,Su, Zhenni,Jiang, Hao,Rong, Jing,Qiu, Xianfan,Tao, Chuanzhou
-
supporting information
p. 843 - 846
(2019/02/19)
-
- Electrochemical synthesis of 1,2-diketones from alkynes under transition-metal-catalyst-free conditions
-
We report an electrochemical protocol for the direct oxidation of internal alkynes in air to provide 1,2-diketones. A variety of functional groups and heterocycle-containing substrates can be tolerated well under mild conditions.
- Zhou, Jie,Tao, Xiang-Zhang,Dai, Jian-Jun,Li, Chen-Guang,Xu, Jun,Xu, Hong-Mei,Xu, Hua-Jian
-
supporting information
p. 9208 - 9211
(2019/08/07)
-
- Rate Enhancement in CAN-Promoted Pd(PPh3)2Cl2-Catalyzed Oxidative Cyclization: Synthesis of 2-Ketofuran-4-carboxylate Esters
-
Stoichiometric ceric ammonium nitrate (CAN) and a catalytic amount of Pd(PPh3)2Cl2 (5 mol %) can rapidly produce multisubstituted 2-ketofuran-4-carboxylate esters from 2-propargylic 1,3-ketoesters via oxidative O-cyclization reaction. Pd(PPh3)2Cl2 was found to be the crucial catalyst as its inclusion greatly enhanced the rate of the reaction and cleanly afforded the products within minutes. Over 30 substrates were successfully converted to the desired compounds in mostly moderate to good yields.
- Ruengsangtongkul, Sureeporn,Chaisan, Nattawadee,Thongsornkleeb, Charnsak,Tummatorn, Jumreang,Ruchirawat, Somsak
-
supporting information
p. 2514 - 2517
(2019/04/30)
-
- One-Pot, Two-Step Metal and Acid-Free Synthesis of Trisubstituted Imidazole Derivatives via Oxidation of Internal Alkynes Using an Iodine/DMSO System
-
A one-pot, two-step, simple, efficient and eco-friendly oxidation of internal alkynes as a key step towards the synthesis of 2,4,5-trisubstituted imidazoles, using an inexpensive I2/DMSO system, has been reported. This metal and acid-free synthesis proceeded smoothly to furnish a variety of synthetically useful trisubstituted imidazoles in moderate to excellent yields. In an effort to demonstrate the potential future applications of this system, a double oxidation study was undertaken and the desired trisubstituted imidazoles obtained in good to moderate yields.
- Naidoo, Shivani,Jeena, Vineet
-
p. 1107 - 1113
(2019/01/04)
-
- Sequentially Pd/Cu-Catalyzed Alkynylation-Oxidation Synthesis of 1,2-Diketones and Consecutive One-Pot Generation of Quinoxalines
-
We report a simple and efficient one-pot synthesis of 1,2-diketones by concatenation of two Pd/Cu-catalyzed processes: Pd0/CuI-catalyzed Sonogashira coupling of terminal alkynes with aryl (pseudo)halides furnishes internal alkynes, which are directly transformed by PdII/CuII-catalyzed Wacker-type oxidation with DMSO and oxygen as dual oxidants to furnish 1,2-diketones. With this efficient, catalyst economical process, various aryl iodides and triflates are efficiently transformed in high yields into symmetrically and unsymmetrically substituted 1,2-diketones with various functional groups. This process can be readily extended to a consecutive one-pot synthesis of quinoxalines in a diversity-oriented fashion.
- Niesobski, Patrik,Martínez, Ivette Santana,Kustosz, Sebastian,Müller, Thomas J. J.
-
supporting information
p. 5214 - 5218
(2019/07/31)
-
- Metal-Free Iodine-Catalyzed Oxidation of Ynamides and Diaryl Acetylenes into 1,2-Diketo Compounds
-
Metal-free oxidation of ynamides is described, employing pyridine-N-oxides as oxidants under molecular iodine catalysis. In stark contrast to Br?nsted acid catalysis, iodophilic activation of ynamides diverts the reaction manifold into a dioxygenation pathway. This oxidation is very rapid at room temperature with only 2.5 mol % I2. Furthermore, this protocol could be extended to nonactivated alkynes, such as diarylacetylenes, to deliver various benzil derivatives.
- Kim, Seung Woo,Um, Tae-Woong,Shin, Seunghoon
-
supporting information
p. 4703 - 4711
(2018/04/26)
-
- Synthetic method of 1,2-diketone compound
-
The invention discloses a synthetic method of a 1,2-diketone compound. The method comprises the following steps: under room temperature, an alkyne compound is taken as a raw material, a Ru/C is takenas a catalyst, an oxidizing agent and sulfuric acid are added, acetonitrile and water with a volume ratio being 1-5:1 are taken as solvents, the materials are completely reacted at the temperature of20-30 DEG C, and a reaction solution is subjected to separating and purifying to obtain the 1,2-diketone compound. The method has the advantages that operation is simple, reaction time is short, yield(achieving to 100%) is high, substrate universality is wide, water and acetonitrile are taken as the primary solvents (the solvent acetonitrile is easily recovered and used), and a heterogeneous phase catalyst Ru/C is easily recovered. The synthetic method of the 1,2-diketone compound accords with green chemistry characteristic, and is very suitable for industrialization.
- -
-
Paragraph 0031-0034
(2018/06/14)
-
- An iodine/DMSO-catalyzed sequential one-pot approach to 2,4,5-trisubstituted-1H-imidazoles from α-methylene ketones
-
A sequential one-pot approach to 2,4,5-trisubstituted imidazoles has been developed from α-methylene ketones and aldehydes. This methodology employs air-moisture stable reaction conditions and an inexpensive iodine/DMSO system affording a diverse range of known and novel (substrate scope) 2,4,5-trisubstituted imidazoles in moderate to excellent yields. The iodine/DMSO system was extended to the domino convergent synthesis of two functionalized intermediates, benzil and benzaldehyde, to produce the final product.
- Jayram, Janeeka,Jeena, Vineet
-
p. 37557 - 37563
(2018/11/26)
-
- Two-Step One-Pot Synthesis of Unsymmetrical (Hetero)Aryl 1,2-Diketones by Addition-Oxygenation of Potassium Aryltrifluoroborates to (Hetero)Arylacetonitriles
-
An efficient one-pot two-step procedure for the synthesis of unsymmetrical (hetero)aryl 1,2-diketones has been developed. The reaction proceeds through a palladium-catalyzed nucleophilic addition of potassium aryltrifluoroborates to aliphatic nitriles followed by a copper-catalyzed aerobic benzylic C–H oxygenation using molecular oxygen as a green oxidant. This represents the first example of the direct synthesis of unsymmetrical diaryl 1,2-diketones from arylacetonitriles. This method utilizes inexpensive, stable, nontoxic, and readily available starting materials, is highly effective in the presence of both electron-rich and electron-poor nitriles and aryltrifluoroborates, and tolerates a wide variety of functional groups. The synthetic utility of this transformation was shown by increasing the scale of the reaction and by carrying out the one-pot protocol for the preparation of quinoxaline and benzimidazole derivatives. A plausible reaction mechanism has also been proposed.
- Kumar, Yogesh,Jaiswal, Yogesh,Kumar, Amit
-
p. 494 - 505
(2018/02/09)
-
- Preparing method of photocatalytic alpha-diketone compound
-
The invention belongs to the technical field of medical and chemical intermediates and related chemicals, and provides a preparing method of photocatalytic alpha-diketone compound. Phenylacetylene and the derivative thereof are used as raw materials, and under the lighting condition, under the combined action of a semiconductor photocatalyst and an additive, alpha-diketone compound is generated through air oxygen in organic solvent. The preparing method has the advantages of being easy to operate, mild in condition and environmentally friendly, has probability of industrialization and obtains the alpha-diketone compound at the high yield, and the catalyst is recyclable. The alpha-diketone compound synthesized through the method can be further functionalized to obtain various compounds applied to development and research of natural products, function materials and fine chemicals.
- -
-
Paragraph 0047-0049
(2017/08/28)
-
- Identification and Mechanistic Evaluation of Hemozoin-Inhibiting Triarylimidazoles Active against Plasmodium falciparum
-
In a previous study, target based screening was carried out for inhibitors of β-hematin (synthetic hemozoin) formation, and a series of triarylimidazoles were identified as active against Plasmodium falciparum. Here, we report the subsequent synthesis and testing of derivatives with varying substituents on the three phenyl rings for this series. The results indicated that a 2-hydroxy-1,3-dimethoxy substitution pattern on ring A is required for submicromolar parasite activity. In addition, cell-fractionation studies revealed uncommonly large, dose-dependent increases of P. falciparum intracellular exchangeable (free) heme, correlating with decreased parasite survival for β-hematin inhibiting derivatives.
- Wicht, Kathryn J.,Combrinck, Jill M.,Smith, Peter J.,Hunter, Roger,Egan, Timothy J.
-
supporting information
p. 201 - 205
(2017/03/08)
-
- Tandem and chemoselective synthesis of benzil derivatives from styrene and arene diazonium salts
-
A facile and practically applied protocol for synthesis of benzil derivatives using styrene and arene diazonium salts is reported. Pd(OAc)2/SeO2 catalytic system was found to be efficient for chemoselective synthesis of benzil. Selenium dioxide works well as an oxidant under milder reaction conditions. Moderate to very good yields of the desired products were obtained.
- Jadhav, Vilas G.,Sarode, Sachin A.,Nagarkar, Jayashree M.
-
supporting information
p. 1834 - 1838
(2017/04/21)
-
- Copper-catalyzed TEMPO oxidative cleavage of 1,3-diketones and β-keto esters for the synthesis of 1,2-diketones and α-keto esters
-
A copper-catalyzed efficient and practical method has been developed for the synthesis of 1,2-diketones and α-keto esters. TEMPO was used as a radical initiator and scavenger, oxidizing the cleavage of α-methylene of 1,3-diketones and β-keto esters to form 1,2-diketones and α-keto esters. This method provided a general way for the formation of 1,2-dicarbonyl compounds.
- Zhou, Peng-Jun,Li, Cheng-Kun,Zhou, Shao-Fang,Shoberu, Adedamola,Zou, Jian-Ping
-
p. 2629 - 2637
(2017/04/03)
-
- An aryl dione the synthetic method of the compound of
-
The invention relates to a synthesis method of an aryldione compound shown in the formula (III). The synthesis method comprises that a compound shown in the formula (I) and a compound shown in the formula (II) undergo a reaction in an organic solvent in the presence of a catalyst, an oxidizing agent and an assistant to produce the compound shown in the formula (III). In the formula, R1 and R2 respectively represent H, C1-C6 alkyl or halogen. Through reasonable selection and combination of the catalyst, the oxidizing agent, the assistant and the organic solvent, a product yield is high. The synthesis method is novel method for synthesis of the aryldione compound and has a good industrial application value and a good industrial production potential.
- -
-
Paragraph 0046-0049; 0063; 0073; 0074; 0082; 0083; 0091
(2018/02/04)
-
- Synthesis of 1,2-Diketones via a Metal-Free, Visible-Light-Induced Aerobic Photooxidation of Alkynes
-
1,2-Diketones were synthesized by the oxidation of corresponding alkynes using air as the oxidant under metal-free conditions upon irradiation of blue light. A cheap and readily available organic dye, eosin Y, was used as the photocatalyst. For various substituents on the aryl ring, the reaction proceeded smoothly to give the dicarbonylation products in moderate to good yields. Some oxidation-sensitive groups, such as formyl and the carbon-carbon double bond, were tolerated under the developed reaction conditions.
- Liu, Xu,Cong, Tiantian,Liu, Ping,Sun, Peipei
-
p. 7256 - 7261
(2016/08/30)
-
- Oxidative Cleavage of Styrenes Catalyzed by a PdIIComplex of an 8-Hydroxyquinolinonate Ligand
-
Synthesis and catalytic activity of palladium complexes of 8-(pyridin-2-ylmethoxy)quinolinone (3) were investigated. Complexation of 3 with [Pd(CH3CN)2Cl2] gave the dimeric palladium complex [{N,N-(3)PdCl}2] (4). The structure of 4 was characterized by1H/13C NMR spectroscopy and mass spectrometry, and further confirmed by X-ray crystallography. Complex 4 acts as a catalyst for oxidative cleavage of C=C bonds, and it catalyzes the hydration of styrenes in an anti-Markovnikov Wacker manner to give terminal aldehydes as the initial product, which then undergo C–C cleavage to yield the corresponding benzaldehydes. Systematic studies of this catalysis were performed.
- Jhong, Hong-Ming,Liu, Yi-Hung,Peng, Shie-Ming,Liu, Shiuh-Tzung
-
p. 5449 - 5455
(2016/12/16)
-
- A method for synthesizing derivatives benzil
-
The invention discloses a method for synthesizing a benzil derivative. The method comprises the following steps: adding epoxy chalcone compound shown in the formula I, a Selectfluor oxidizing agent and inorganic base into a mixed solvent of acetonitrile and water, stirring for reaction for 4-8 h at 60-100 DEG C, and treating a reaction liquid obtained after the reaction is finished to prepare the benzil derivative shown in the formula II. The synthesis method has the advantages that the raw materials are cheap and easy to obtain, transition metal catalysis is not needed, the oxygen source is easy to obtain and environment-friendly, the reaction condition is mild, the target substrate can be synthesized efficiently, the universality of the functional group is good, and the operation is simple and convenient.
- -
-
Paragraph 0045-0048
(2020/02/07)
-
- Preparation method of 1,2-diketone derivative
-
The invention discloses a preparation method of a 1,2-diketone derivative. The method comprises the step of enabling a raw material 1,3-diketone derivative to react with a cheap and easily obtained industrial product 2,2,6,6-tetramethyl-1-piperidinyloxy under the catalysis of copper so as to obtain the product 1,2-diketone derivative. According to the preparation method, the 1,3-diketone derivative is used as an initiator, and the raw material is easy to obtain and wide in variety; by utilizing the preparation method, the obtained product types are varied, can be directly used, and can be used for other further reactions; in addition, the reagent dosage in the reaction is less, the pollution is reduced, and the production cost is lowered; moreover the reaction conditions are mild, the reaction operation and the after-treatment process are simple, the reaction time is short, the yield is high, and the preparation method is suitable for industrial production.
- -
-
Paragraph 0020
(2016/10/08)
-
- Method for preparing dibenzol derivative
-
The invention discloses a method for preparing a dibenzol derivative. The synthesis path of the dibenzol derivative is shown in the description, wherein Ar1 and Ar2 are each selected from phenyl, methyl substituted phenyl, ethyl substituted phenyl, methoxyl substituted phenyl and halogen substituted phenyl. The synthesis process comprises the steps of adding a compound 1, copper chloride dehydrate and lithium bromide into a reaction bottle, adding a reaction solvent for constant-temperature reaction at 30 DEG C in the atmosphere of oxygen under a blue light source, conducting TLC tracking monitoring, and conducting column chromatography isolation after reaction ends to obtain a compound 2. By the adoption of the method, the dibenzol derivative can be prepared in an environment-friendly mode. The method has the advantages that reaction conditions are mild and environment-friendly, cost is low, efficiency is high, reaction path is short, and atom economy is high.
- -
-
Page/Page column 5
(2017/04/19)
-
- Efficient synthetic route to bisaryl ketones via copper-catalyzed C-C triple bonds cleavage
-
An efficient copper-catalyzed aerobic synthesis of bisaryl ketones from 1,2-diarylalkynes via C-C triple bonds cleavage has been demonstrated. The aniline compounds were found to be crucial in our conditions and a plausible mechanism was put forward. This reaction constitutes a new transformation from 1,2-diarylalkynes into bisaryl ketones with a practical, neutral, and mild synthetic approach.
- Li, Xiangguang,Huang, Wenzhong,Liang, Deqiang,Yuan, Lin,Ma, Yinhai,Gu, Lijun
-
p. 1045 - 1049
(2015/01/30)
-
- An unusual chemoselective oxidation strategy by an unprecedented exploration of an electrophilic center of DMSO: A new facet to classical DMSO oxidation
-
A conceptually new dimethyl sulfoxide (DMSO) based oxidation process without the use of any activator has been demonstrated for the oxidation of active methylenes and benzhydrols. The developed protocol utilizes the electrophilic center of DMSO for oxidation, which was unexplored before. Mechanistic investigation has confirmed that the source of oxygen is DMSO.
- Chebolu, Rajesh,Bahuguna, Ashish,Sharma, Reena,Mishra, Vivek Kumar,Ravikumar
-
supporting information
p. 15438 - 15441
(2015/10/20)
-
- Copper-catalyzed base-accelerated direct oxidation of C-H bond to synthesize benzils, isatins, and quinoxalines with molecular oxygen as terminal oxidant
-
We describe herein an efficient and general copper (II)-catalyzed base-accelerated oxidation of the C-H bond to synthesize benzils and isatins. With similar oxidation system an efficient one-pot procedure for the synthesis of quinoxaline derivatives was realized. The two protocols feature using molecular oxygen as terminal oxidant, low catalyst loading, wide substrate scope, and high functional-group tolerance.
- Yu, Jing-Wen,Mao, Shuai,Wang, Yong-Qiang
-
supporting information
p. 1575 - 1580
(2015/03/14)
-
- Selectfluor-Mediated Simultaneous Cleavage of C-O and C-C Bonds in α,β-Epoxy Ketones under Transition-Metal-Free Conditions: A Route to 1,2-Diketones
-
Selectfluor-mediated simultaneous cleavage of C-O and C-C bonds in α,β-epoxy ketones has been successfully achieved under transition-metal-free conditions. The reaction gives 1,2-diketone compounds in moderate to good yields involving a ring-opening/benzoyl rearrangement/C-C bond cleavage sequence under oxidative conditions.
- Wang, Heng,Ren, Shaobo,Zhang, Jian,Zhang, Wei,Liu, Yunkui
-
p. 6856 - 6863
(2015/10/06)
-
- Cobalt(II) catalyzed C(sp)-H bond functionalization of alkynes with phenyl hydrazines: Facile access to diaryl 1,2-diketones
-
A cobalt acetylacetonate catalyzed oxidative diketonation of alkynes via C(sp)-H bond functionalization has been described. The reaction involves a free-radical mechanism, wherein the phenyl radical formed from phenyl hydrazine couples with Co(ii) activated alkyne to produce 1,2-diketones. The reaction proceeds at room temperature in DMF with the use of Ag2O/air as the oxidizing system. The utility of the protocol for the synthesis of a series of imidazoles including a potent platelet aggregation inhibitor trifenagrel has been demonstrated.
- Bharate, Jaideep B.,Abbat, Sheenu,Sharma, Rohit,Bharatam, Prasad V.,Vishwakarma, Ram A.,Bharate, Sandip B.
-
p. 5235 - 5242
(2015/05/13)
-
- Visible-light-induced C=C bond cleavage of enaminones for the synthesis of 1,2-diketones and quinoxalines in sustainable medium
-
The C=C double bond cleavage of enaminones has been realized under ambient conditions through visible-light catalysis in the presence of Rose Bengal, which leads to the synthesis of a class of 1,2-diketones without using any metal catalyst. In addition, the one-pot synthesis of quinoxalines has also been achieved under identical photocatalytic conditions by making use of the in situ generated 1,2-diketones as intermediates.
- Cao, Shuo,Zhong, Shanshan,Xin, Luoting,Wan, Jie-Ping,Wen, Chengping
-
p. 1478 - 1482
(2015/06/24)
-
- Asymmetric transfer hydrogenation of unsymmetrical benzils
-
In this paper, the asymmetric transfer hydrogenation of unsymmetrical benzils with m, p-substituents was conducted with a substrate/catalyst molar ratio of 100 at 40°C for 24 h to produce (S,S)-hydrobenzoins in good yields (76.2% to 97.1%) with high diastereomeric (syn/anti = 10.8 to 29.7/1) and enantiomeric purities (86.1%ee syn to 98.9%ee syn). Unfortunately, the unsymmetrical benzils with the o-substituents such as electron-donating (R = CH3, OCH3) and electron-withdrawing groups (R = F, Cl, CF3) resulted in poor yields (0% to 31.2%), even at 40°C for 72 h. These products had inefficient diastereoselectivities (syn/anti = 1.5 to 5.0/1) caused by steric effects. Furthermore, the results of a dynamic-kinetic study were used to propose a plausible reaction pathway of unsymmetrical benzil using 3-methoxy-1,2-diphenyl ethanedione as an example.
- Zhang, Hao,Feng, Dandan,Sheng, Haibo,Ma, Xuebing,Wan, Jinwei,Tang, Qian
-
p. 6417 - 6423
(2014/02/14)
-
- Ruthenium-catalyzed synthesis of 1,2-diketones from alkynes
-
The ruthenium-catalyzed synthesis of 1,2-diketones through the oxidation of alkynes by using sodium hypochlorite has been investigated. RuO4 was generated in situ from inexpensive RuCl3·xH2O, and NaOCl as the oxidant demonstrated high performance at room temperature in the solvent diethyl carbonate. A variety of diketones were prepared in good yields by using this environmentally friendly procedure.
- Miao, Yanan,Dupe, Antoine,Bruneau, Christian,Fischmeister, Cedric
-
p. 5071 - 5077
(2014/08/18)
-
- N-Heterocyclic carbene-catalyzed double acylation of enones with benzils
-
Thiazolium carbene-catalyzed reaction of aromatic 1,2-diketones with enones in aprotic solvents gave double acylation products in good yields, whereas hydroacylation products formed by Stetter reaction were not detected at all. These results suggested the generation of aroyloxyenamine species from the 1,2-diketones instead of hydroxyenamines (Breslow intermediates). This journal is
- Takaki, Ken,Ohno, Akira,Hino, Makoto,Shitaoka, Takashi,Komeyama, Kimihiro,Yoshida, Hiroto
-
supporting information
p. 12285 - 12288
(2014/12/11)
-
- Copper-mediated aerobic oxidative cleavage of α,β-unsaturated ketones to 1,2-diketones
-
The copper-mediated aerobic oxidative cleavage of α,β- unsaturated ketones to synthesize 1,2-diketones by using potassium acetate as a catalyst and sodium iodide as a promoter in acetic acid is described. The protocol has the advantages of using inexpensive and non-toxic raw materials, high yield and simple work-up procedure. the Partner Organisations 2014.
- Li, Zheng,Yin, Junjun,Wen, Gong,Li, Tianpeng,Shen, Xiaoli
-
p. 32298 - 32302
(2014/08/18)
-
- One-pot, two-step desymmetrization of symmetrical benzils catalyzed by the methylsulfinyl (dimsyl) anion
-
An operationally simple one-pot, two-step procedure for the desymmetrization of benzils is herein described. This consists in the chemoselective cross-benzoin reaction of symmetrical benzils with aromatic aldehydes catalyzed by the methyl sulfinyl (dimsyl) anion, followed by microwave-assisted oxidation of the resulting benzoylated benzoins with nitrate, avoiding the costly isolation procedure. Both electron-withdrawing and electron-donating substituents may be accommodated on the aromatic rings of the final unsymmetrical benzil. the Partner Organisations 2014.
- Ragno, Daniele,Bortolini, Olga,Giovannini, Pier Paolo,Massi, Alessandro,Pacifico, Salvatore,Zaghi, Anna
-
p. 5733 - 5744
(2014/07/22)
-
