939-48-0Relevant articles and documents
Rapid long range intramolecular electron transfer within a steroid molecule with two electron binding groups
Huddleston, R. Kurt,Miller, John R.
, p. 5337 - 5344 (1983)
Intramolecular electron tarnsfer has been observed to have occurred in less than 100 ns in a steroid molecule having two distinct electron binding groups separated by distances distributed from 7-11 Angstroem.Experiments were carried out in organic glasses at 77 K with pulse radiolysis techniques to create trapped electrons which were captured by a group on one end of the steroid molecule.Although one of the groups, benzoate, is held to the steroid spacer by a flexible linkage, the rigidity of the glassy matrices prevented movement to alter the initial distance.Interestingly, no effects of distance were seen: all ET processes appeared to have occurred much faster than our 100 ns time resolution, consistent with measurements of the rate of intermolecular electron transfer between the same functional groups in random solutions.Solvation energetics, on the other hand, had a remarkable influence on the extent and direction of electron transfer.A change in solvent polarity was observed to reverse the direction of electron transfer.Evidence was obtained for a distribution of solvation environments for ions in glasses which may be as broad as 0.15 eV.
Electrochemical esterification via oxidative coupling of aldehydes and alcohols
Smeyne, Dylan,Verboom, Katherine,Bryan, Maria,LoBue, James,Shaikh, Abid
supporting information, (2021/03/26)
An electrolytic method for the direct oxidative coupling of aldehydes with alcohols to produce esters is described. Our method involves anodic oxidation in presence of TBAF as supporting electrolyte in an undivided electrochemical cell equipped with graphite electrodes. This method successfully couples a wide range of alcohols to benzaldehydes with yields ranging from 70 to 90%. The protocol is easy to perform at a constant voltage conditions and offers a sustainable alternative over conventional methods.
Direct Amidation of Esters by Ball Milling**
Barreteau, Fabien,Battilocchio, Claudio,Browne, Duncan L.,Godineau, Edouard,Leitch, Jamie A.,Nicholson, William I.,Payne, Riley,Priestley, Ian
supporting information, p. 21868 - 21874 (2021/09/02)
The direct mechanochemical amidation of esters by ball milling is described. The operationally simple procedure requires an ester, an amine, and substoichiometric KOtBu and was used to prepare a large and diverse library of 78 amide structures with modest to excellent efficiency. Heteroaromatic and heterocyclic components are specifically shown to be amenable to this mechanochemical protocol. This direct synthesis platform has been applied to the synthesis of active pharmaceutical ingredients (APIs) and agrochemicals as well as the gram-scale synthesis of an active pharmaceutical, all in the absence of a reaction solvent.
PCl3-mediated transesterification and aminolysis of tert-butyl esters via acid chloride formation
Wu, Xiaofang,Zhou, Lei,Li, Fangshao,Xiao, Jing
, p. 491 - 497 (2021/01/20)
A PCl3-mediated conversion of tert-butyl esters into esters and amides in one-pot under air is developed. This novel protocol is highlighted by the synthesis of skeletons of bioactive molecules and gram-scale reactions. Mechanistic studies revealed that this transformation involves the formation of an acid chloride in situ, which is followed by reactions with alcohols or amines to afford the desired products.
Metal nitrate-catalyzed one-pot oxidative esterification of benzaldehyde with hydrogen peroxide in alcoholic solutions at room temperature
Da Silva, Márcio José,De Oliveira, Cesar Macedo
, p. 3683 - 3691 (2021/03/03)
The activity of metal nitrate catalysts was investigated in the oxidative esterification reactions of benzaldehyde with hydrogen peroxide. Several types of metal nitrates (alkaline, alkaline earth, and transition metals) were evaluated as catalysts. Among the assessed salts, Fe(NO3)3 was the most efficient catalyst toward the formation of the target product (i.e., benzoic alkyl ester). In methyl alcohol, benzaldehyde was selectively oxidized to benzoic acid and then esterified to methyl benzoate. The efficiency of the catalyst was correlated with its higher Lewis acidity character, which was established through the pH measurements of methanolic solutions of the soluble metal nitrate salts. The influence of main variables of the reaction, such as catalyst load, temperature, and reactant stoichiometry, was investigated. The size of the carbon chain and steric hindrance played an essential role in the reaction selectivity. While methyl and ethyl alcohols selectively provided ester as the main product (ca. 70-75%) and acetal as the subproduct, the other alcohols gave ester, hemiacetal, and benzoic acid, which was formed in the least amount. The use of an inexpensive catalyst, a green oxidant, mild conditions, and short reaction times were the positive aspects of this one-pot process. The high TON (ca. 900) is evidence of the high catalytic activity of Fe(NO3)3. It is noteworthy that this methodology does not rely upon ligands and other additives.
Oxidative esterification of alcohols by a single-side organically decorated Anderson-type chrome-based catalyst
Wang, Jingjing,Jiang, Feng,Tao, Chaofu,Yu, Han,Ruhlmann, Laurent,Wei, Yongge
supporting information, p. 2652 - 2657 (2021/04/21)
The direct esterification of alcohols with non-noble metal-based catalytic systems faces great challenges. Here, we report a new chrome-based catalyst stabilized by a single pentaerythritol decorated Anderson-type polyoxometalate, [N(C4H9)4]3[CrMo6O18(OH)3C{(OCH2)3CH2OH}], which can realize the efficient transformation from alcohols to esters by H2O2oxidation in good yields and high selectivity without extra organic ligands. A variety of alcohols with different functionalities including some natural products and pharmaceutical intermediates are tolerated in this system. The chrome-based catalyst can be recycled several times and still keep the original configuration and catalytic activity. We also propose a reasonable catalytic mechanism and prove the potential for industrial applications.
Uranyl(VI) Triflate as Catalyst for the Meerwein-Ponndorf-Verley Reaction
Kobylarski, Marie,Monsigny, Louis,Thuéry, Pierre,Berthet, Jean-Claude,Cantat, Thibault
supporting information, p. 16140 - 16148 (2021/11/01)
Catalytic transformation of oxygenated compounds is challenging in f-element chemistry due to the high oxophilicity of the f-block metals. We report here the first Meerwein-Ponndorf-Verley (MPV) reduction of carbonyl substrates with uranium-based catalysts, in particular from a series of uranyl(VI) compounds where [UO2(OTf)2] (1) displays the greatest efficiency (OTf = trifluoromethanesulfonate). [UO2(OTf)2] reduces a series of aromatic and aliphatic aldehydes and ketones into their corresponding alcohols with moderate to excellent yields, using iPrOH as a solvent and a reductant. The reaction proceeds under mild conditions (80 °C) with an optimized catalytic charge of 2.3 mol % and KOiPr as a cocatalyst. The reduction of aldehydes (1-10 h) is faster than that of ketones (>15 h). NMR investigations clearly evidence the formation of hemiacetal intermediates with aldehydes, while they are not formed with ketones.
N-Aroylbenzotriazoles as Efficient Reagents for o-Aroylation in Absence of Organic Solvent
Hahnvajanawong, Viwat,Phungpis, Baramee
, p. 2671 - 2674 (2021/10/25)
N-Aroylbenzotriazoles have been shown to be efficient reagents for esterification in the absence of organic solvent. Grinding of N-aroylbenzoytiazoles with twofold excess of alcohols for a couple of hours at room temperature gave corresponding esters in high percentage of yields.
Manganese-Mediated C-C Bond Formation: Alkoxycarbonylation of Organoboranes
Van Putten, Robbert,Filonenko, Georgy A.,Krieger, Annika M.,Lutz, Martin,Pidko, Evgeny A.
supporting information, p. 674 - 681 (2021/04/02)
Alkoxycarbonylations are important and versatile reactions that result in the formation of a new C-C bond. Herein, we report on a new and halide-free alkoxycarbonylation reaction that does not require the application of an external carbon monoxide atmosphere. Instead, manganese carbonyl complexes and organo(alkoxy)borate salts react to form an ester product containing the target C-C bond. The required organo(alkoxy)borate salts are conveniently generated from the stoichiometric reaction of an organoborane and an alkoxide salt and can be telescoped without purification. The protocol leads to the formation of both aromatic and aliphatic esters and gives complete control over the ester's substitution (e.g., OMe, OtBu, OPh). A reaction mechanism was proposed on the basis of stoichiometric reactivity studies, spectroscopy, and DFT calculations. The new chemistry is particularly relevant for the field of Mn(I) catalysis and clearly points to a potential pathway toward irreversible catalyst deactivation.
Soluble asphaltene oxide: A homogeneous carbocatalyst that promotes synthetic transformations
Bielawski, Christopher W.,Jung, Hyosic
, p. 15598 - 15603 (2020/05/05)
Carbocatalysts, materials which are predominantly composed of carbon and catalyze the synthesis of organic or inorganic compounds, are promising alternatives to metal-based analogues. Even though current carbocatalysts have been successfully employed in a broad range of synthetic transformations, they suffer from a number of drawbacks in part due to their heterogeneous nature. For example, the insolubility of prototypical carbocatalysts, such as graphene oxide (GO), may restrict access to catalytically-active sites in a manner that limits performance and/or challenges optimization. Herein we describe the preparation and utilization of soluble asphaltene oxide (sAO), which is a novel material that is composed of oxidized polycyclic aromatic hydrocarbons and is soluble in a wide range of organic solvents as well as in aqueous media. sAO promotes an array of synthetically useful transformations, including esterifications, cyclizations, multicomponent reactions, and cationic polymerizations. In many cases, sAO was found to exhibit higher catalytic activities than its heterogeneous analogues and was repeatedly and conveniently recycled, features that were attributed to its ability to form homogeneous phases.
