- Mechanistic insight into the synergistic Cu/Pd-catalyzed carbonylation of aryl iodides using alcohols and dioxygen as the carbonyl source
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Pd-catalyzed carbonylation, as an efficient synthetic approach to the installation of carbonyl groups in organic compounds, has been one of the most important research fields in the past decade. Although elegant reactions that allow highly selective carbonylations have been developed, straightforward routes with improved reaction activity and broader substrate scope remain long-term challenges for new practical applications. Here, we show a new type of synergistic Cu/Pd-catalyzed carbonylation reaction using alcohols and dioxgen as the carbonyl sources. A broad range of aryl iodides and alcohols are compatible with this protocol. The reaction is concise and practical due to the ready availability of the starting materials and the scalability of the reaction. In addition, the reaction affords lactones and lactams in an intermolecular fashion. Moreover, DFT calculations have been performed to study the detailed mechanisms. [Figure not available: see fulltext.]
- Li, Junxuan,Zhou, Jinlei,Wang, Yumei,Yu, Yue,Liu, Qiang,Yang, Tilong,Chen, Huoji,Cao, Hua
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- Zr-MOF-808 as Catalyst for Amide Esterification
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In this work, zirconium-based metal–organic framework Zr-MOF-808-P has been found to be an efficient and versatile catalyst for amide esterification. Comparing with previously reported homogeneous and heterogeneous catalysts, Zr-MOF-808-P can promote the reaction for a wide range of primary, secondary and tertiary amides with n-butanol as nucleophilic agent. Different alcohols have been employed in amide esterification with quantitative yields. Moreover, the catalyst acts as a heterogeneous catalyst and could be reused for at least five consecutive cycles. The amide esterification mechanism has been studied on the Zr-MOF-808 at molecular level by in situ FTIR spectroscopic technique and kinetic study.
- Villoria-del-álamo, Beatriz,Rojas-Buzo, Sergio,García-García, Pilar,Corma, Avelino
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supporting information
p. 4588 - 4598
(2020/12/25)
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- A Straightforward Conversion of Activated Amides and Haloalkanes into Esters under Transition-Metal-Free Cs 2 CO 3 /DMAP Conditions
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The esterification of activated amides, N -acylsaccharins, under transition-metal-free conditions with good functional group tolerance has been developed, resulting in C-N cleavage leading to efficient synthesis of a variety of esters in moderate to good yields. This work demonstrates that esterification may proceed by using simple N -acylsaccharins, haloalkanes, and Cs 2 CO 3 as oxygen source.
- Chen, Liuqing,Gu, Ying,Jian, Junsheng,Liu, Yueping,Miao, Liqiong,Wang, Zijia,Zeng, Zhuo
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p. 4078 - 4084
(2019/10/28)
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- Synthetic method of an ester compound
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The invention discloses a synthetic method of an ester compound and belongs to the technical field of organic synthesis. The synthetic method includes the steps of: dissolving an aldehyde compound (1) and a halogenated hydrocarbon compound (2) in a solvent, adding an oxidant and a catalyst, and performing a reaction at 60-100 DEG C to obtain the target product ester compound (3). A reaction equation of the synthetic method is represented as follows. The method, compared with the prior art, has the following advantages: 1) the raw materials are easy to obtain and are low in cost; 2) the reaction conditions are mild, operations are simple, and reaction time is short; and 3) a substrate has wide available range and can be used for synthesis of various ester compounds.
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Paragraph 0063; 0064; 0065
(2017/02/02)
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- Fe-Catalyzed Aerobic Oxidative C-CN Bond Cleavage of Arylacetonitriles Leading to Various Esters
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Fe-catalyzed aerobic oxidative esterifications of arylacetonitriles with alcohols, tri alkoxsilanes, silicate esters, or borate esters have been developed. The acyl groups which were in situ generated via chemoselective C(CO)-CN bond cleavage were directly used as electrophiles, leading to corresponding aryl esters in good to excellent yields under molecular oxygen when attacked by alcohols or alcohol surrogates. Dioxygen serves as both oxidant and reactant in this protocol. The reaction has a very broad substrate scope. Cheap starting materials as well as environmentally benign and inexpensive iron catalyst and ideal oxidant O2 feature this transformation and make it a practical and sustainable protocol to afford esters.
- Kong, Weiguang,Li, Bingnan,Xu, Xuezhao,Song, Qiuling
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p. 8436 - 8443
(2016/09/28)
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- Generally applicable and efficient esterification of aldehydes with alcohols catalyzed by cyclopalladated ferrocenylimine
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The palladacycle-catalyzed esterification of a variety of aldehydes with alcohols was developed. This reaction allows formation of esters in moderate to excellent yields not only for various aldehydes but also alcohols. In addition, the esterification could proceed well under mild conditions with a low catalyst loading of 0.0625 mol%. Copyright
- Ma, Gaizhi,Leng, Yuting,Qiao, Huijie,Yang, Fan,Wang, Shiwei,Wu, Yangjie
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- Combined catalytic system of scandium triflate and boronic ester for amide bond cleavage
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We have found that the combination of scandium with boronic ester enables the cleavage of amide bonds. Primary amides were converted to the corresponding esters in the presence of catalytic amounts of scandium triflate and boronic ester under mild and neutral conditions. This unique catalytic system can be applied to the deprotection of acetylaniline derivatives. In addition, control NMR experiments were carried out to examine the effect of the boronic esters. Copyright
- Kita, Yusuke,Nishii, Yuji,Onoue, Akihiro,Mashima, Kazushi
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supporting information
p. 3391 - 3395
(2013/12/04)
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- Electrochemical reduction of phthalide at carbon cathodes in dimethylformamide: Effects of supporting electrolyte and gas chromatographic injector-port chemistry on the product distribution
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Cyclic voltammetry and controlled-potential (bulk) electrolysis have been used to investigate the direct reduction of phthalide at carbon electrodes in dimethylformamide (DMF) containing 0.10 M tetramethylammonium perchlorate (TMAP) or tetra-n-butylammonium perchlorate (TBAP). Cyclic voltammograms recorded with a glassy carbon electrode exhibit a single cathodic peak and a corresponding anodic peak that arise, respectively, from one-electron reduction of phthalide to generate a radical-anion intermediate and from reoxidation of the intermediate. At a scan rate of 100 mV s-1, quasi-reversible behavior is observed (due to ring-opening of the radical-anion), whereas fully reversible behavior is seen at 5 V s-1 or higher. Digital simulation of cyclic voltammograms indicates that the lifetime of the radical-anion is 3.5 s. Bulk electrolysis of phthalide at a reticulated vitreous carbon cathode affords products that depend on the procedure used to analyze the catholyte. Direct injection of catholyte into a gas chromatograph shows phthalide and a 2-methylbenzoate ester bearing an alkyl moiety from the supporting-electrolyte cation. However, if the catholyte is partitioned between diethyl ether and aqueous hydrochloric acid before gas chromatographic analysis, phthalide and 2-methylbenzoic acid are observed. Thermally induced reactions that occur in the injector port of the gas chromatograph are responsible for the formation of the 2-methylbenzoate ester as well as for the phthalide found in all electrolyzed solutions.
- Pasciak, Erick M.,Hochstetler, Spencer E.,Mubarak, Mohammad S.,Evans, Dennis H.,Peters, Dennis G.
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p. 557 - 563
(2013/11/19)
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- Fe3O4 supported Pd(0) nanoparticles catalyzed alkoxycarbonylation of aryl halides
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This paper describes the simple and efficient method for the alkoxycarbonylation of aryl iodides using magnetically recoverable Pd/Fe 3O4 as the catalyst under atmospheric pressure of carbon monoxide. Various aryl iodides on alkoxycarbonylation with alcohols gave the corresponding products in good to excellent yields. The catalyst is completely recoverable with the simple application of an external magnetic field, and the efficiency of the catalyst remains unaltered even after five cycles.
- Siva Prasad, Aviraboina,Satyanarayana, Bollikonda
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p. 205 - 209
(2013/04/23)
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- Zinc-catalyzed amide cleavage and esterification of β- hydroxyethylamides
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Snipping tool: Zn(OTf)2 is an efficient catalyst for selective cleavage of amides bearing a β-hydroxyethyl group on the nitrogen atom. The mechanism involves an N,O-acyl rearrangement and transesterification. This new catalytic system can be applied to sequence-specific peptide bond scission at the amine side of a serine residue. Tf=trifluoromethanesulfonyl. Copyright
- Kita, Yusuke,Nishii, Yuji,Higuchi, Takafumi,Mashima, Kazushi
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supporting information; experimental part
p. 5723 - 5726
(2012/08/07)
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- Ligand free palladium catalyzed decarboxylative cross-coupling of aryl halides with oxalate monoester salts
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Ligand free Pd-catalyzed decarboxylative cross-coupling of potassium oxalate monoester and derivatives with aryl iodides and bromides is described. Functionalized aromatic esters can be efficiently synthesized via this method with only 1.0 mol % Pd(OAc)2 catalyst without any phosphine ligand. This method illustrates an inexpensive and operationally simple method for the preparation of aromatic esters and acids, which is especially beneficial for a large scale synthesis.
- Li, Yan,Chen, Huan-Huan,Wang, Chu-Fei,Xu, Xiao-Lan,Feng, Yi-Si
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p. 5796 - 5799
(2012/10/29)
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- Synthesis of tert-butyl peroxyacetals from benzyl, allyl, or propargyl ethers via iron-promoted C-H bond functionalization
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When benzyl, allyl, and propargyl ethers were treated with tert-butyl hydroperoxide and a catalytic amount of iron(III) acetylacetonate, tert-butyl peroxyacetals were produced in good to excellent yields, via C-H bond functionalization. This method is also applicable to ethylene acetals of unsaturated aldehydes to give peroxyorthoesters.
- Iwata, Satoshi,Hata, Takeshi,Urabe, Hirokazu
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supporting information
p. 3480 - 3484
(2013/02/22)
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- An improved protocol for palladium-catalyzed alkoxycarbonylations of aryl chlorides with alkyl formates
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The palladium-catalyzed alkoxycarbonylation of aryl and heteroaryl halides using butyl formate has been investigated. In the presence of palladium (II) acetate/n-butylbis(1-adamantyl)phosphine (L1), and l,8-diazabicyclo[5.4.0]undec- 7-ene (DBU) as base fo
- Schareina, Thomas,Zapf, Alexander,Cotte, Alain,Gotta, Matthias,Beller, Matthias
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experimental part
p. 1205 - 1209
(2010/07/04)
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- Palladium-catalyzed aerobic oxidative carbonylation of arylboronate esters under mild conditions
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(Figure Presented) "CO"n Air: The title reaction was carried out using [PdCl2(PPh3)2 ] as the catalyst precursor under very mild conditions (balloon pressure of CO and air, at 40- 50°C), and produced a wide range of aryl carboxyl esters 2 in good to excellent yields. Remarkable selectivity between oxidative carbonylation and homocoupling of arylboronate esters l was also achieved.
- Liu, Qiang,Li, Gang,He, Jun,Liu, Jing,Li, Peng,Lei, Aiwen
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supporting information; experimental part
p. 3371 - 3374
(2010/07/06)
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- Catalytic processes of oxidation by hydrogen peroxide in the presence of Br2 or HBr. Mechanism and synthetic applications
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The mechanism and the synthetic applications for the oxidation of alcohols, ethers, and aldehydes by H2O2 catalyzed by Bf2 or Br- in a liquid two-phase system (aqueous and organic) are reported. Aliphatic and benzylic primary alcohols and ethers show an opposite behavior, which has been rationalized on the ground of the different electronic configurations of the intermediate alkyl (π-type) and acyl (σ-type) radicals and their influence on enthalpic and polar effects. A two-phase system is particularly useful also for an efficient benzylic bromination by Br2 or Br-; the substitution of the benzyl bromide by OH, OR, and OCOR regenerates Br-, which can be recycled. The evaluation of the relative reactivities of the involved substrates and intermediates has allowed to develop a variety of simple, facile, convenient, and selective syntheses of alcohols, aldehydes, ketones, esters, and benzyl bromides, which fulfill the conditions for practical applications.
- Amati, Alessandro,Dosualdo, Gabriele,Zhao, Lihua,Bravo, Anna,Fontana, Francesca,Minisci, Francesco,Bjorsvik, Hans-Rene
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p. 261 - 269
(2013/09/08)
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