- 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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- KPF6-Mediated Esterification and Amidation of Carboxylic Acids
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A novel KPF6-promoted green method has been developed for the synthesis of esters and amides. A wide range of carboxylic acids and alcohols or amines worked well under the developed reaction conditions, thus providing good to excellent (61-98%) yields of
- Sonam, None,Shinde, Vikki N.,Kumar, Anil
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p. 2651 - 2661
(2022/02/07)
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- Practical: In situ -generation of phosphinite ligands for palladium-catalyzed carbonylation of (hetero)aryl bromides forming esters
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An effective method for alkoxycarbonylation of (hetero)aryl bromides is developed in the presence of in situ-generated phosphinite ligands tBu2POR (R = nBu, nPr, Et or Me). For this purpose commercially available tBu2PCl was used as the pre-ligand in the presence of different alcohols. For the first time cross coupling reactions with two alcohols-one generating the ligand, the other used as substrate-were developed. Through this method, ligand optimization can be performed in a more efficient manner and the desired products could be obtained with good yields and selectivity.
- Wang, Lin,Neumann, Helfried,Spannenberg, Anke,Beller, Matthias
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supporting information
p. 7469 - 7472
(2017/07/12)
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- Synthesis of naphthalenecarboxylic and naphthalenedicarboxylic acids from naphthalene, carbon tetrachloride, and alcohols in the presence of iron catalysts
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Alkyl naphthalenecarboxylates and dialkyl naphthalenedicarboxylates have been synthesized by reactions of naphthalene and its derivatives with alcohols and carbon tetrachloride in the presence of iron catalysts.
- Baiguzina,Erokhina,Khusnutdinov
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p. 389 - 395
(2017/05/01)
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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 0081; 0082; 0083
(2017/02/02)
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- Expedient carbonylation of aryl halides in aqueous or neat condition
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An expedient and versatile, microwave-assisted procedure for the carbonylation of aryl halides with boronic acids, alcohols or amines in water or under neat conditions has been developed. The reaction is catalyzed by fluorous, oxime-based palladacycle 1 that shows an excellent recyclable property and low levels of Pd leaching. To demonstrate the usefulness of the protocol, we applied it to the preparation of compounds of pharmaceutical interest, including a precursor of the reverse transcriptase inhibitor, niacin, benzocaine and butamben.
- Ang, Wei Jie,Lo, Lee-Chiang,Lam, Yulin
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p. 8545 - 8558
(2014/12/11)
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- One-pot transformation of carboxylic acids into nitriles
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A variety of aromatic and aliphatic carboxylic acids were smoothly converted into the corresponding nitriles in good yields in a one-pot procedure by treatment with ethyl iodide/K2CO3/18-crown-6, followed by sodium diisobutyl-tert-butoxyaluminium hydride (SDBBA-H), and finally treatment with molecular iodine or 1,3-diiodo-5,5-dimethylhydantoin (DIH), and aqueous ammonia. This method is useful for the conversion of various aromatic and aliphatic carboxylic acids into the corresponding nitriles in a one-pot procedure. A variety of aromatic and aliphatic carboxylic acids were smoothly converted into the corresponding nitriles in good yields in a one-pot procedure by treatment with ethyl iodide/K2CO3/18-crown-6, followed by sodium diisobutyl-tert-butoxyaluminium hydride (SDBBA-H), and finally treatment with molecular iodine or 1,3-diiodo-5,5-dimethylhydantoin (DIH), and aqueous ammonia. Copyright
- Miyagi, Kotaro,Moriyama, Katsuhiko,Togo, Hideo
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p. 5886 - 5892
(2013/09/23)
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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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- Efficient carbonylation of aryl and heteroaryl bromides under atmospheric pressure of CO
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In the presence of Et and n-BuOH, efficient alkoxycarbonylation of (hetero)aromatic bromides was achieved under atmospheric pressure of carbon monoxide with in situ generated palladium/rac-BINAP as catalyst. Georg Thieme Verlag Stuttgart - New York.
- Yang, Weizhun,Han, Wei,Zhang, Weidong,Shan, Lei,Sun, Jiansong
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supporting information; experimental part
p. 2253 - 2255
(2011/10/19)
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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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- Conformationally gated fragmentations and rearrangements promoted by interception of the bergman cyclization through intramolecular H-abstraction: A possible mechanism of auto-resistance to natural enediyne antibiotics?
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A variety of fragmentations and rearrangements can follow Bergman cyclization in enediynes equipped with acetal rings mimicking the carbohydrate moiety of natural enediyne antibiotics of the esperamicine and calchiamicine families. In the first step of all these processes, intramolecular H-atom abstraction efficiently intercepts the p-benzyne product of the Bergman cyclization through a six-membered TS and transforms the p-benzyne into a new more stable radical. Depending on the substitution pattern and reaction conditions, this radical follows four alternative paths: (a) abstraction of an external hydrogen atom, (b) O-neophyl rearrangement which transposes O- and C-atoms of the substituent, (c) fragmentation of the O-C bond in the acetal ring, or (d) fragmentation with elimination of the appended acetal moiety as a whole. Experiments with varying concentrations of external H-atom donor (1,4-cyclohexadiene) were performed to gain further insight into the competition between intermolecular H-abstraction and the fragmentations. The Thorpe-Ingold effect in gem-dimethyl substituted enediynes enhances the efficiency of fragmentation to the extent where it cannot be prevented even by a large excess of external H-atom donor. These processes provide insight into a possible mechanism of unusual fragmentation of esperamicin A1 upon its Bergman cycloaromatization and lay foundation for a new approach for the conformational control of reactivity of these natural antitumor antibiotics. Such an approach, in conjunction with supramolecular constraints, may provide a plausible mechanism for resistance to enediyne antibiotics by the enediyne-producing microorganisms.
- Baroudi, Abdulkader,Mauldin, Justin,Alabugin, Igor V.
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supporting information; experimental part
p. 967 - 979
(2010/03/31)
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- N-Heterocyclic carbene-catalyzed oxidations
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N-Heterocyclic carbenes catalyze the oxidation of allylic and benzylic alcohols as well as saturated aldehydes to esters with manganese(IV) oxide in excellent yields. A variety of esters can be synthesized, including protected carboxylates. The oxidation proceeds under mild conditions, with low loadings of a simple triazolium salt pre-catalyst in the presence of base. Substrates containing potentially epimerizable centers are oxidized while preserving stereochemical integrity. The acyl triazolium intermediate generated under catalytic conditions can be employed as a chiral acylating agent in the desymmetrization of meso-diols.
- Maki, Brooks E.,Chan, Audrey,Phillips, Eric M.,Scheidt, Karl A.
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experimental part
p. 3102 - 3109
(2009/09/05)
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- Studies in Acyl C-H activation via aryl and alkyl to acyl "through space" migration of palladium
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Examples of the 1,4-migration of a palladium moiety in aryl- and alkylpalladium intermediates to the acyl position of an aldehyde or formamide have been observed. The resulting acylpalladium intermediate can undergo ester or carbamate formation by reaction with an alcohol; decarbonylation, followed by β hydride elimination to an alkene; reaction with an organomercurial to form an ester; or alkene insertion. Deuterium-labeling studies have been used to confirm the palladium migration mechanism.
- Kesharwani, Tanay,Verma, Akhilesh K.,Emrich, Daniel,Ward, Jeffrey A.,Larock, Richard C.
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supporting information; experimental part
p. 2591 - 2593
(2009/10/23)
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- Copper-catalyzed synthesis of esters from ketones. Alkyl group as a leaving group
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The conversion of ketones to esters has been achieved through the use of Cu catalyst and tetrabutylammonium nitrite. This reaction involves the activation of the less activated C-C bond, and the alkyl group is removed as a leaving group. Various isopropyl ketones are found to be good substrates for this reaction.
- Nakatani, Yuji,Koizumi, Yuichiro,Yamasaki, Ryu,Saito, Shinichi
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supporting information; experimental part
p. 2067 - 2070
(2009/04/08)
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- Tandem oxidation of allylic and benzylic alcohols to esters catalyzed by N-heterocyclic carbenes
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(Chemical Equation Presented) N-Heterocyclic carbenes catalyze the oxidation of allylic, propargylic, and benzylic alcohols to esters with manganese(IV) oxide in excellent yields. A variety of ester derivatives can be synthesized, including protected carboxylates. This one-pot tandem oxidation represents the first organocatalytic oxidation of alcohols to esters. Saturated esters can also be accessed from aldehydes using this method. Through the utilization of a chiral catalyst, the acyl-heteroazolium intermediate becomes a chiral acylating agent, which can desymmetrize meso-1,2-diols.
- Maki, Brooks E.,Chan, Audrey,Phillips, Eric M.,Scheidt, Karl A.
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p. 371 - 374
(2007/10/03)
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- Alumina sulfuric acid as a novel heterogeneous system for esterification of carboxylic acids in solvent free conditions
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Neat chlorosulfonic acid reacts with alumina to give alumina sulfuric acid (ASA) in which sulfuric acid is immobilised on the surface of alumina via a covalent bond. Carboxylic acids can be readily converted to their corresponding esters with a combination of ASA and alcohols in solvent free conditions.
- Sharghi, Hashem,Sarvari, Mona Hosseini,Eskandari, Razieh
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p. 488 - 491
(2007/10/03)
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- Butoxycarbonylation of aryl halides catalyzed by a silica-supported poly[3-(2-cyanoethylsulfanyl)propylsiloxane palladium] complex
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Aryl bromides and iodides react with carbon monoxide and n-butyl alcohol at 100°C and atmospheric pressure in the presence of tri-n-butylamine and a catalytic amount of a silica-supported sulfur palladium complex to form esters in moderate to good yields.
- Cai, Ming-Zhong,Song, Cai-Sheng,Huang, Xian
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p. 2273 - 2274
(2007/10/03)
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- Palladium-catalyzed Desulfonylative Carbonylation of Arylsulfonyl Chlorides in the Presence of Titanium Tetraalkoxides
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The carbonylation of arylsulfonyl chlorides with a catalytic amount of tetrakis(triphenylphosphine)palladium(0) in the presence of a titanium tetraalkoxide gives the corresponding esters along with diaryl disulfides.
- Miura, Masahiro,Itoh, Kenji,Nomura, Masakatsu
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- Mono- and Bi-metallic Catalysed Formate-Halide Carbonylation Reactions
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Benzylic, aryl, and alkyl halides react with formate esters and carbon monoxide, in the presence of the dimer of chloro(hexa-1,5-diene)rhodium(I), 2, to give carboxylic esters: bimetallic catalysis 2> is particularly beneficial when an aromatic halide is used as the substrate.
- Buchan, Caroline,Hamel, Nathalie,Woell, James B.,Alper, Howard
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p. 167 - 168
(2007/10/02)
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- PALLADIUM(0) AND RHODIUM(I) CATALYSIS OF THE CARBONYLATION OF UNACTIVATED BROMIDES
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Alkyl, vinyl, and aromatic bromides react with organoborates and carbon monoxide, in the presence of catalytic quantities of 1,5-hexadienerhodium(I) chloride dimer and tetrakis(triphenylphosphine)palladium(0), to give carboxylic esters in good yields.
- Hashem, Khaled E.,Woell, James B.,Alper, Howard
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p. 4879 - 4880
(2007/10/02)
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- Process for the preparation of carboxylic acid esters from organic halides
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Carboxylic acid esters or amides are obtained from aryl, heterocyclic, vinylic, ethynylic, and benzylic halides and substituted derivates thereof, by reacting same with an alcohol or primary or secondary amine and carbon monoxide, in the presence of a palladium catalyst and if necessary a tertiary amine at about 20°-150° C and from about a half to about 100 atmospheres pressure. A typical example is the conversion of bromobenzene into n-butyl benzoate at 100° C and one atmosphere of carbon monoxide in the presence of tri-n-butyl-amine and a catalytic amount of PdBr2 [P(C6 H5)3 ]2.
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