37542-28-2Relevant academic research and scientific papers
Tris(pentafluorophenyl)borane-Catalyzed Oxygen Insertion Reaction of α-Diazoesters (α-Diazoamides) with Dimethyl Sulfoxide
Gao, Wen-Xia,Liu, Miao-Chang,Wu, Hua-Yue,Wu, Xiao-Yang,Zhou, Yun-Bing
supporting information, (2022/01/19)
A tris(pentafluorophenyl)borane-catalyzed oxidation reaction of α-diazoesters (α-diazo amides) with dimethyl sulfoxide has been developed. The reaction proceeds under metal free conditions to afford a series α-ketoesters and α-ketoamides. The synthetic utility of this protocol is demonstrated through synthetic transformations and scaled-up synthesis. (Figure presented.).
Unraveling two pathways for NHPI-mediated electrocatalytic oxidation reaction
Xu, Leitao,Yi, Yangjie,Hu, Sideng,Ye, Jiao,Hu, Aixi
, (2021/11/30)
Two pathways for N-hydroxyphthalimide (NHPI)-mediated electrocatalytic oxidation using phenylacetate derivatives as template substrates were first reported for benzylic C[sbnd]H oxidation to oxygenated and non-oxygenated products. DFT calculation indicates that the hydrogen-atom transfer (HAT) process between phthalimido-N-oxyl (PINO) and substrate is a rate-determined step. Aromatic α-keto esters and 2-((1,3-dioxoisoindolin-2-yl)oxy)-2-aryl acetate obtained by cross-coupling between benzylic radical and PINO can be selectively synthesized through controlling the concentration of PINO radical. This method provides a deep understanding for selective weak C[sbnd]H oxidation using NHPI as redox mediator.
Photoinduced Diverse Reactivity of Diazo Compounds with Nitrosoarenes
Roy, Sourav,Kumar, Gourav,Chatterjee, Indranil
supporting information, p. 6709 - 6713 (2021/09/08)
A diverse reactivity of diazo compounds with nitrosoarene in an oxygen-transfer process and a formal [2 + 2] cycloaddition is reported. Nitosoarene has been exploited as a mild oxygen source to oxidize an in situ generated carbene intermediate under visible-light irradiation. UV-light-mediated in situ generated ketenes react with nitosoarenes to deliver oxazetidine derivatives. These operationally simple processes exemplify a transition-metal-free and catalyst-free protocol to give structurally diverse α-ketoesters or oxazetidines.
Visible-Light-Induced Catalyst-Free Carboxylation of Acylsilanes with Carbon Dioxide
Fan, Zhengning,Yi, Yaping,Chen, Shenhao,Xi, Chanjuan
supporting information, p. 2303 - 2307 (2021/04/05)
Intermolecular carbon-carbon bond formation between acylsilanes and carbon dioxide (CO2) was achieved by photoirradiation under catalyst-free conditions. In this reaction, siloxycarbenes generated by photoisomerization of the acylsilanes added to the C═O bond of CO2 to give α-ketocarboxylates, which underwent hydrolysis to afford α-ketocarboxylic derivatives in good yields. Control experiments suggest that the generated siloxycarbene is likely to be from the singlet state (S1) of the acylsilane and the addition to CO2 is not in a concerted manner.
[Fe(bpy)3]2+-based porous organic polymers with boosted photocatalytic activity for recyclable organic transformations
Liu, Hong-Kun,Lei, Yi-Fei,Tian, Peng-Ju,Wang, Hui,Zhao, Xin,Li, Zhan-Ting,Zhang, Dan-Wei
supporting information, p. 6361 - 6367 (2021/03/22)
Three rigid metal porous organic polymers (POPs) based on an iron(ii) complex are prepared from the condensation reactions of an octahedral [Fe(bpy)3]2+-cored hexaaldehyde and three rod-like aromatic diamines. The POPs have been studied as the first series of earth-abundant metal complex-connected photocatalysts for heterogeneous visible light-driven oxidation of benzyl halides and enantioselective α-alkylation of aldehydes. Both yields and enantioselectivities of the reactions catalyzed by one of the POPs, which possesses the largest porosity, rival or even surpass those of the reactions homogeneously catalyzed by control [Fe(bpy)3]2+complexes. Moreover, POP catalysts are highly stable and exhibit a considerable activity after recycling 10 times.
Tandem Photoredox-Chiral Phosphoric Acid Catalyzed Radical-Radical Cross-Coupling for Enantioselective Synthesis of 3-Hydroxyoxindoles
Zhang, Yang,Ye, Dan,Shen, Lei,Liang, Kangjiang,Xia, Chengfeng
supporting information, p. 7112 - 7117 (2021/09/14)
A photochemical protocol that couples diarylamines and α-ketoesters to afford the chiral 3-hydroxyoxindoles through tandem photoredox and chiral phosphoric acid catalysis is developed. The reaction involves an enantioselective photochemical radical-radical cross-coupling process. The chiral phosphoric acid is discovered to play crucial roles by decreasing the reductive potentials of α-ketoesters and stereocontrolling the downstream asymmetric radical-radical cross-coupling via the formation of pentacoordinate complex.
Methyl Benzoylformate Derivative Norrish Type I Photoinitiators for Deep-Layer Photocuring under Near-UV or Visible LED
He, Xianglong,Gao, Yanjing,Nie, Jun,Sun, Fang
, p. 3854 - 3864 (2021/05/07)
We designed and prepared a series of methyl benzoylformate (MBF) derivatives Norrish type I photoinitiators (MBFs) for light-emitting diode (LED)-induced photopolymerization through computer simulation. The potential photolysis mechanism of MBFs under LED at 405 nm was explored by steady-state photolysis, nuclear magnetic resonance, and electron spin resonance. The as-synthesized photoinitiator dimethyl 1,4-dibenzoylformate (DM-BD-F) can efficiently initiate free radical photopolymerization of acrylate monomers under LED irradiation at 405 nm. Moreover, we predicted well the photoinitiating capability of MBFs through the cleavage exothermy (ΔH) calculated by triplet bond dissociation energy (BDE) and triplet energy (ET). Significantly, based on the weak absorption of MBFs at 405 nm, MBFs were successfully applied to deep-layer photocuring and the curing depth reached 6.5 cm after the irradiation of LED at 405 nm for 30 s. This research provides a new idea and efficient strategy for the molecular design of photoinitiators for deep-layer photocuring.
Green preparation method of aryl [alpha]-keto ester compound
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Paragraph 0061-0064, (2020/05/30)
The invention discloses a green preparation method of an aryl [alpha]-keto ester compound. The method comprises the specific steps that an [alpha]-diazo compound serves as a reaction raw material, copper sulfate serves as a catalyst, water serves as a solvent, a target product aryl [alpha]-keto ester compound is prepared through a reaction at the temperature of 60 DEG C, the structural general formula of the [alpha]-diazo compound is shown in the specification, and the structural general formula of the correspondingly prepared target product aryl [alpha]-keto ester compound is shown in the specification. The method for synthesizing the target product aryl [alpha]-keto ester compound by catalyzing the [alpha]-diazo compound derivative with copper sulfate has the advantages that the reactioncondition is green and mild, the catalyst is cheap and easy to obtain, the operation is simple and convenient, the yield is relatively high, the universality of a reaction substrate is wide, and thelike.
Copper(I)-catalyzed aerobic oxidation of α-diazoesters
Xu, Changming,Bai, Lei,Wang, Yongchang
, p. 12579 - 12584 (2020/11/09)
A practical Cu-catalyzed oxidation of α-diazoesters to α-ketoesters using molecular oxygen as an oxidant has been developed. Both electron-poor and electron-rich aryl α-diazoesters are suitable substrates and provide the α-ketoesters in good yields. In this oxidative system, α-diazo-β-ketoesters are also compatible as substrates but unexpectedly furnish α-ketoesters via C-C bond cleavage, rather than the vicinal tricarbonyl products.
Novel synthesis method of alpha-carbonyl acid ester
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Paragraph 0016; 0068; 0072-0073, (2020/07/21)
The invention discloses a novel synthesis method of alpha-carbonyl acid ester. The method comprises the following steps: carrying out chlorination reaction on an alpha-methylene-containing nitrile compound and chlorine to obtain dichloronitrile, reacting the dichloronitrile product in a sulfuric acid and water system to obtain formyl cyanide, then acquiring an imino sulfate compound in the same reaction system, and finally performing esterification to obtain the target product. The adopted reaction raw materials are wide in sources and low in price, highly toxic solid sodium cyanide can be prevented from being used in the prior art, the method is environmentally friendly, and the method is easy to operate, mild in condition and easy to industrialize.
