19115-34-5Relevant academic research and scientific papers
Silver-catalyzed functionalization of esters by carbene transfer: The role of ylide zwitterionic intermediates
Gava, Riccardo,Fuentes, M. Angeles,Besora, Maria,Belderrain, Tomas R.,Jacob, Kane,Maseras, Feliu,Etienne, Michel,Caballero, Ana,Perez, Pedro J.
, p. 2206 - 2210 (2014)
The reaction of esters with ethyl diazoacetate catalyzed by the complex [F27-Tp4Bo,3CF2CF3Ag(acetone)] generates α-(acyloxy)acetates in moderate to high yields. This is a novel transformation in the context of carbene-transfer reactions from diazo compounds that, according to experimental and theoretical data, is suggested to occur through zwitterionic intermediates.
Kinetics of reaction of triethylammonium carboxylates with ethyl α-halogenoacetate in various solvents
Krishna Pillay,Ganesan
, p. 894 - 900 (1999)
The kinetics of the reaction of ethyl α-halogenoacetate with benzoic acid in the presence of triethylamine in aqueous acetone and in various solvents have been investigated. The rate constant of the reaction is 4-260 times higher in aprotic dipolar solvents than in protic solvents. The simple regression and multiple regression of log k2 with various solvent parameters have led to the conclusion that in addition to the solvent polarity, various other solvent properties, together or individually, influence the reaction rate.
Tropylium-Catalyzed O-H Insertion Reactions of Diazoalkanes with Carboxylic Acids
Empel, Claire,Nguyen, Thanh Vinh,Koenigs, Rene M.
supporting information, p. 548 - 553 (2021/01/26)
Herein, we describe the application of a nonbenzenoid aromatic carbocation, namely tropylium, as an organic Lewis acid catalyst in O-H functionalization reactions of diazoalkanes with benzoic acids. The newly developed protocol is applicable to a wide range of diazoalkane and carboxylic acid substrates with excellent efficiency (43 examples, up to 99% yield).
An Acid Stable Metal-Organic Framework as an Efficient and Recyclable Catalyst for the O?H Insertion Reaction of Carboxylic Acids
Wang, Yingxia,Cui, Hao,Zhang, Li,Su, Cheng-Yong
, p. 3901 - 3906 (2018/08/01)
Although metal-organic frameworks (MOFs) can be used in many reactions, their applications in acid involved reactions are limited due to their instability in acid environment. As a stable MOF, the Ir(III)-porphyrin metal-organic framework of the formula [(Hf6(μ3-O)8(OH)2(H2O)10)2(Ir(TCPP)Cl)3]?solvents (Ir-PMOF-1(Hf)) can sustain its structure upon treatments in different pH (0–11) aqueous solutions. In this work, Ir-PMOF-1(Hf) has been examined in the O?H insertion reaction of carboxylic acids with diazo compounds. Catalytic results show that as low as 0.042 mol % of Ir-PMOF-1(Hf) can promote the acid O?H insertion with the maximum turn over number (TON) of 1381, and furthermore, it can be recycled and reused for 10 runs, suggesting that Ir-PMOF-1(Hf) is efficient for this acid involved reaction. Ir-PMOF-1(Hf) can also be miniaturized to nano scale (diameter range of 400–500 nm), and a large improvement with regards to TON (8400) can be observed in its catalysis.
In situ generation of nitrilium from nitrile ylide and the subsequent Mumm rearrangement: copper-catalyzed synthesis of unsymmetrical diacylglycine esters
Chen, Jijun,Shao, Ying,Ma, Liang,Ma, Meihua,Wan, Xiaobing
supporting information, p. 10723 - 10732 (2016/11/30)
A novel in situ generation of nitrilium from a nitrile ylide and the subsequent Mumm rearrangement of carboxylic acid, nitrile, and diazo compounds gave various unsymmetrical diacylglycine esters in moderate to high yields. This copper-catalyzed cascade reaction enables one-pot generation of two C-N bonds, one C=O bond, and one C-H bond, with nitrogen as the only byproduct. The reaction has a broad functional-group tolerance, is rapid, easily scales up to the 100 mmol scale, and is insensitive to air and moisture.
I2-catalyzed regioselective oxo- and hydroxy-acyloxylation of alkenes and enol ethers: A facile access to α-acyloxyketones, esters, and diol derivatives
Reddi, Rambabu N.,Prasad, Pragati K.,Sudalai, Arumugam
supporting information, p. 5674 - 5677 (2015/02/19)
I2-catalyzed oxo-acyloxylation of alkenes and enol ethers with carboxylic acids providing for the high yield synthesis of α-acyloxyketones and esters is described. This unprecedented regioselective oxidative process employs TBHP and Et3/s
Nonmetal catalyzed insertion reactions of diazocarbonyls to acid derivatives in fluorinated alcohols
Dumitrescu, Lidia,Azzouzi-Zriba, Kaouther,Bonnet-Delpon, Daniele,Crousse, Benoit
supporting information; experimental part, p. 692 - 695 (2011/04/24)
The insertion reaction of diazocarbonyls to acids could be performed smoothly in fluorinated alcohols in the absence of metal catalyst. This new procedure allowed the chemoselective preparation of various functionalized compounds such as acyloxyesters, depsipeptides, and sulfonate, phosphonate, or boronate derivatives.
The Separation of Polar and Steric Effects in the Reaction of ortho-Substituted Benzoate Ions with Ethyl Bromoacetate
Srinivasan, Chockalingam,Shunmugasundaram, Arunachalam,Arumugam, Natesan
, p. 213 - 216 (2007/10/02)
The second-order rate coefficients for the reactions of ortho-substituted benzoate ions with ethyl bromoacetate have been measured in a 90percent acetone-10percent water (v/v) mixture at three different temperatures and the results have been compared with those of phenacyl bromide.The order of reactivity of ortho-substituted benzoate ions with ethyl bromoacetate is almost the same as that observed for the reaction of ortho-substituted benzoate ions with phenacyl bromide.Attempts have been made to analyse the rate data in terms of electronic and steric effects by employing Charton's treatment.Analysis of the results shows that the localized effect is predominant over the delocalized effect in each reaction series and electron-releasing groups favour the reaction and electron-withdrawing groups retard it.The steric term is rate accelerating.The ΔS(excit.) values for all the ortho-substituted benzoate ions are negative and it appears that the bulk effect of the substituent plays a part in the variation of ΔS(excit.).
REARRANGEMENT OF α-ACYLOXYACETATES INTO 2-HYDROXY-3-KETOESTERS
Lee, S. D.,Chan, T. H.,Kwon, K. S.
, p. 3399 - 3402 (2007/10/02)
α-Acyloxyacetates rearrange under LDA conditions to give 2-hydroxy-3-ketoesters.The corresponding trimethylsilyl- or acetyl derivatives can be obtained by quenching the reaction mixture with Me3SiCl or Ac2O.
Kinetics of Reaction of Halo Esters: Part II - Reactivity of Ethyl Bromoacetate towards Substituted trans-Cinnamate Ions
Srinivasan, C.,Shunmugasundaram, A.,Arumugam, N.
, p. 355 - 356 (2007/10/02)
The rates of reactions of several substituted trans-cinnamate and acrylate ions with ethyl bromoacetate in 90percent acetone-10percent water (v/v) have been measured at 303, 308 and 313 K.A good Hammett correlation is obtained for trans-cinnamate ions with ρ = -0.181 at 308 K.Correlation with non-aromatic trans-3-substituted acrylate ions is poor.There is an apparent failure of reactivity-selectivity principle in this case possibly due to a slightly modified transition state.
