86358-28-3Relevant academic research and scientific papers
Nature of the Nucleophilic Oxygenation Reagent Is Key to Acid-Free Gold-Catalyzed Conversion of Terminal and Internal Alkynes to 1,2-Dicarbonyls
Dubovtsev, Alexey Yu.,Shcherbakov, Nikolay V.,Dar'in, Dmitry V.,Kukushkin, Vadim Yu.
, p. 745 - 757 (2020/02/04)
2,3-Dichloropyridine N-oxide, a novel oxygen transfer reagent, allows the conductance of the gold(I)-catalyzed oxidation of alkynes to 1,2-dicarbonyls in the absence of any acid additives and under mild conditions to furnish the target species, including those derivatized by highly acid-sensitive groups. The developed strategy is effective for a wide range of alkyne substrates such as terminal- and internal alkynes, ynamides, alkynyl ethers/thioethers, and even unsubstituted acetylene (40 examples; yields up to 99%). The oxidation was successfully integrated into the trapping of reactive dicarbonyls by one-pot heterocyclization and into the synthesis of six-membered azaheterocycles. This synthetic acid-free route was also successfully applied for the total synthesis of a natural 1,2-diketone.
B2pin2-mediated copper-catalyzed oxidation of alkynes into 1,2-diketones using molecular oxygen
Zhai, Yadong,Su, Zhenni,Jiang, Hao,Rong, Jing,Qiu, Xianfan,Tao, Chuanzhou
supporting information, p. 843 - 846 (2019/02/19)
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.
Two-Step One-Pot Synthesis of Unsymmetrical (Hetero)Aryl 1,2-Diketones by Addition-Oxygenation of Potassium Aryltrifluoroborates to (Hetero)Arylacetonitriles
Kumar, Yogesh,Jaiswal, Yogesh,Kumar, Amit
, p. 494 - 505 (2018/02/09)
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.
CO2-assisted synthesis of non-symmetric α-diketones directly from aldehydes: Via C-C bond formation
Hirapara, Pradipbhai,Riemer, Daniel,Hazra, Nabanita,Gajera, Jignesh,Finger, Markus,Das, Shoubhik
supporting information, p. 5356 - 5360 (2017/11/22)
CO2-assisted various symmetric and non-symmetric α-diketones have been synthesized directly from the corresponding aldehydes using transition metal-free catalysts. This method can even be applied to synthesize pharmaceuticals directly from aldehydes. The crucial role of CO2 has been investigated in detail and the mechanism is proposed on the basis of experiments and DFT calculations.
Copper-catalyzed TEMPO oxidative cleavage of 1,3-diketones and β-keto esters for the synthesis of 1,2-diketones and α-keto esters
Zhou, Peng-Jun,Li, Cheng-Kun,Zhou, Shao-Fang,Shoberu, Adedamola,Zou, Jian-Ping
, p. 2629 - 2637 (2017/04/03)
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.
Preparation method of 1,2-diketone derivative
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Paragraph 0034, (2016/10/08)
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.
A Desulfonylative Approach in Oxidative Gold Catalysis: Regiospecific Access to Donor-Substituted Acyl Gold Carbenes
Chen, Hongyi,Zhang, Liming
supporting information, p. 11775 - 11779 (2015/10/05)
Donor-substituted acyl gold carbenes are challenging to access selectively by gold-promoted intermolecular oxidation of internal alkynes as the opposite regioisomers frequently predominate. By using alkynyl sulfones or sulfonates as substrates, the oxidative gold catalysis in the presence of substituted pyridine N-oxides offers regiospecific access to acyl/aryl, acyl/alkenyl, and acyl/alkoxy gold carbenes by in situ expulsion of sulfur dioxide. The intermediacies of these reactive species are established by their reactivities, including undergoing further oxidation by the same oxidant, cyclopropanation of styrenes, engaging in a [3+2] cycloaddition with α-methylstyrene, and conversion into dienones. Accept it: A desulfonylative approach was developed to regiospecifically access these underexplored acyl gold carbenes from either alkynyl aryl/alkenyl sulfones or alkynyl sulfonate substrates. The reactivities of these donor- and acceptor-substituted carbenes are examined.
Readily available ruthenium complex for efficient dynamic kinetic resolution of aromatic α-hydroxy ketones
Agrawal, Santosh,Martinez-Castro, Elisa,Marcos, Rocio,Martin-Matute, Belen
supporting information, p. 2256 - 2259 (2014/05/06)
A ruthenium complex formed from commercially available [Ru(p-cymene)Cl 2]2 and 1,4-bis(diphenylphosphino)butane catalyzes the racemization of aromatic α-hydroxy ketones very efficiently at room temperature. The racemization is fully compatible with a kinetic resolution catalyzed by a lipase from Pseudomonas stutzeri. This is the first example of dynamic kinetic resolution of α-hydroxy ketones at ambient temperature in which the metal and enzyme catalysts work in concert in one pot at room temperature to give quantitative yields of esters of α-hydroxy ketones with very high enantioselectivity.
One-pot, two-step desymmetrization of symmetrical benzils catalyzed by the methylsulfinyl (dimsyl) anion
Ragno, Daniele,Bortolini, Olga,Giovannini, Pier Paolo,Massi, Alessandro,Pacifico, Salvatore,Zaghi, Anna
, p. 5733 - 5744 (2014/07/22)
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.
Ruthenium-catalyzed oxidation of alkenes at room temperature: A practical and concise approach to α-diketones
Chen, Shulin,Liu, Zhaojun,Shi, Erbo,Chen, Long,Wei, Wei,Li, Hong,Cheng, Yannan,Wan, Xiaobing
supporting information; experimental part, p. 2274 - 2277 (2011/06/27)
Chemical equations presented. The catalytic oxidation of alkenes to α-diketones is unprecedented. A new oxidation of alkenes, catalyzed by a ruthenium complex, which allows an efficient route to α-diketones using TBHP as an oxidant is described. This methodology is highly functional group tolerant, is practically convenient, requires no additional ligand, and operates under mild conditions with short reaction times. Based upon experimental observations, a plausible mechanism is proposed.
