- 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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- IrIII-Catalyzed direct syntheses of amides and esters using nitriles as acid equivalents: A photochemical pathway
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An unprecedented IrIII[df(CF3)ppy]2(dtbbpy)PF6-catalyzed simple photochemical process for direct addition of amines and alcohols to the relatively less reactive nitrile triple bond is described herein. Various amides and esters are synthesized as the reaction products, with nitriles being the acid equivalents. A mini-library of different types of amides and esters is made using this mild and efficient process, which uses only 1 mol% of photocatalyst under visible light irradiation (λ = 445 nm). The reaction strategy is also efficient for gram-scale synthesis.
- Talukdar, Ranadeep
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supporting information
p. 5303 - 5308
(2020/04/17)
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- Cross-Dehydrogenating Coupling of Aldehydes with Amines/R-OTBS Ethers by Visible-Light Photoredox Catalysis: Synthesis of Amides, Esters, and Ureas
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A straightforward synthesis of amides, ureas, and esters is reported by visible-light cross-dehydrogenating coupling (CDC) of aldehydes (or amine carbaldehydes) and amines/R-OTBS ethers by photoredox catalysis. The reaction is found to be general and high yielding. A plausible mechanistic pathway has been proposed for these transformations and is supported by appropriate controlled experiments.
- Pandey, Ganesh,Koley, Suvajit,Talukdar, Ranadeep,Sahani, Pramod Kumar
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supporting information
p. 5861 - 5865
(2018/09/21)
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- Synthesis and structures of 1,2,4-triazoles derivatives
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Abstract A series of novel 1,2,4-triazole derivatives were synthesized, and their structures were characterized by IR, UV-Vis, FL, NMR, ESI-MS, and elemental analysis. In the meanwhile, the single crystal structures of 3,4-diethyl-5-(4-pyridyl)-1,2,4-triazole and 3,4-dimethyl-5-(o-hydroxyphenyl)-1,2,4-triazole were determined by X-ray diffraction.
- Wang, Ning,Sheng, Jun-Feng,Song, Fei,Tong, Yu-Zhu,Wang, Zuo-Xiang
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p. 746 - 751
(2015/05/05)
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- Ionic liquids provide unique opportunities for oral drug delivery: Structure optimization and in vivo evidence of utility
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Ionic liquids (ILs) have been exploited to improve the absorption of poorly water-soluble drugs. Custom-made ILs solubilized very high quantities of the poorly water-soluble drugs, danazol and itraconazole, and maintained drug solubilization under simulated gastro-intestinal conditions. A danazol-containing self-emulsifying IL formulation gave rise to 4.3-fold higher exposure than the crystalline drug and prolonged exposure compared with a lipid formulation.
- Williams, Hywel D.,Sahbaz, Yasemin,Ford, Leigh,Nguyen, Tri-Hung,Scammells, Peter J.,Porter, Christopher J. H.
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supporting information
p. 1688 - 1690
(2014/02/14)
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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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- LUBRICANT COMPOSITIONS CONTAINING A HETEROAROMATIC COMPOUND
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An ashless additive for lubricating oil compositions, lubricating oil compositions and methods for lubricating that are effective to improve the total base number (TBN) of a lubricant composition. The additive is a reaction product of a compound of the formula: with NH3, an alcohol, an amine, or a hydrocarbyl amine, wherein R1 is selected from H, a hydrocarbyl group, the alcohol or amine contains from 1 to about 24 carbon atoms, and the hydrocarbyl amine has a number average molecular weight ranging from about 100 to about 6000
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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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- Synthesis and catalytic applications of stable palladium dioxygen complexes
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The synthesis and characterization of air-stable palladium dioxygen complexes Pd(O2)L2 of basic phosphines L = P(1-Ad) 2nBu, PtBu2nBu is described. Contrary to general belief, these dioxygen complexes are stable catalyst precursors for palladium-catalyzed coupling reactions. Specifically, palladium-catalyzed formylations and alkoxy carbonylations of aryl bromides proceed in high yield in air using commercial non-degassed solvents. It is shown that Pd(O2)L2 complexes are reduced back to the catalytically active palladium(0) species in the reductive atmosphere of CO or H2 at the onset of the carbonylation reaction.
- Sergeev, Alexey G.,Neumann, Helfried,Spannenberg, Anke,Beller, Matthias
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experimental part
p. 3368 - 3373
(2010/10/04)
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- Sonogashira coupling reactions in biodegradable ionic liquids derived from nicotinic acid
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The biodegradable ionic liquids, 3-butoxycarbonyl-1-methylpyridinium bis(trifluoromethanesulfonyl)imides (1a-d), have been evaluated as solvents for copper- and phosphine-free Sonogashira coupling reactions. The stability of these ionic liquids toward basic conditions was analysed in order to further probe their utility for transition metal catalyzed reactions which require the presence of a base.
- Harjani, Jitendra R.,Abraham, Theodore J.,Gomez, Alwyn T.,Garcia, M. Teresa,Singer, Robert D.,Scammells, Peter J.
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experimental part
p. 650 - 655
(2010/08/22)
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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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- Biodegradable pyridinium ionic liquids: Design, synthesis and evaluation
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A range of ionic liquids (ILs) with a pyridinium cation were synthesised and their biodegradability was evaluated using the CO2 Headspace test (ISO 14593). ILs bearing an ester side chain moiety were prepared from either pyridine or nicotinic acid and showed high levels of biodegradation under aerobic conditions and can be classified as 'readily biodegradable'. In contrast, pyridinium ILs with alkyl side chains showed significantly lower levels of biodegradability in the same test. The utility of the biodegradable IL 6c as a reaction solvent for the Diels-Alder reaction was also investigated.
- Harjani, Jitendra R.,Singer, Robert D.,Garcia, M. Teresa,Scammells, Peter J.
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experimental part
p. 83 - 90
(2010/04/22)
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- Palladium-catalyzed carbonylation of aryl tosylates and mesylates
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A general protocol for the palladium-catalyzed carbonylation of aryl tosylates and mesylates to form esters has been developed using a catalyst system derived from Pd(OAc)2 and the bulky, bidentate dcpp ligand. The system operates under mild conditions: atmospheric CO pressure and temperatures of 80-110 °C. A broad substrate scope has been demonstrated allowing carbonylation of electron-rich, electron-poor, and heterocyclic tosylates and mesylates, and the reaction shows wide functional group tolerance. Copyright
- Munday, Rachel H.,Martinelli, Joseph R.,Buchwald, Stephen L.
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p. 2754 - 2755
(2008/09/19)
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- New cyclopentadienyl, indenyl or fluorenyl substituted phosphine compounds and their use in catalytic reactions
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The invention is directed to a phosphine compound represented by general formula (1) wherein R' and R" independently are selected from alkyl, cycloalkyl and 2-furyl radicals, or R' and R" are joined together to form with the phosphorous atom a carbon-phosphorous monocycle comprising at least 3 carbon atoms or a carbon-phosphorous bicycle; the alkyl radicals, cycloalkyl radicals, and carbon-phosphorous monocycle being unsubstituted or substituted by at least one radical selected from the group of alkyl, cycloalkyl, aryl, alkoxy, and aryloxy radicals; Cps is a partially substituted or completely substituted cyclopentadien-1-yl group, including substitutions resulting in a fused ring system, and wherein a substitution at the 1-position of the cyclopentadien-1-yl group is mandatory when the cyclopentadien-1-yl group is not part of a fused ring system or is part of an indenyl group. Also claimed is the use of these phosphines as ligands in catalytic reactions and the preparation of these phosphines.
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Page/Page column 64; 65; 66
(2008/06/13)
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- Carbonylation of aryl chlorides with oxygen nucleophiles at atmospheric pressure. Preparation of phenyl esters as acyl transfer agents and the direct preparation of alkyl esters and carboxylic acids
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(Chemical Equation Presented) A mild, functional group tolerant method of the preparation of phenyl esters from aryl chlorides via palladium-catalyzed carbonylation is described using atmospheric pressure of carbon monoxide. Phenyl esters are shown to be useful acylating agents, delivering libraries of carbonyl derivatives, including alkyl, allyl and thioesters, under very mild conditions. Direct preparation of alkyl esters and carboxylic acids is also demonstrated, providing the first method for the preparation of methyl and ethyl esters from aryl chlorides without pressured reactors.
- Watson, Donald A.,Fan, Xuexiang,Buchwald, Stephen L.
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supporting information; experimental part
p. 7096 - 7101
(2009/05/09)
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- Inhibitory effect of 3-carboethoxypyridine and 3-carbobutoxypyridine on isolated rat uterus
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3-Carbomethoxypyridine (CMP) was isolated and characterized from the leaves of Pyrenacantha staudtii Hutch and Dalz, family Icacinaceae, in our earlier study and was found to possess an inhibitory activity on the isolated rat uterus. In order to study the structure - activity relationship, derivatives of CMP were obtained synthetically, purified and characterized by spectroscopic techniques such as infra red spectroscopy (IR), nuclear magnetic resonance (1H- and 13C-NMR) and mass spectrometry (MS). The synthesized compounds were subjected to pharmacological testing using isolated rat uterine preparation in oestrus suspended in an organ bath containing De Jalon physiological salt solution (PSS). The force of contraction was recorded via an isometric transducer connected to an Ugo Basile recorder. The effects of these two compounds were compared with salbutamol as a positive control. 3-Carboethoxypyridine (ECP) demonstrated very significant (p 0.005) inhibitory activity on the uterus with a total elimination of the spontaneous contractility at a dose of 0.4 mg/mL. Carbobutoxypyridine (BCP) also demonstrated a marked reduction of oxytocin-induced contractions and elimination of spontaneous activity. The study lends support to the potential use of these agents as tocolytics.
- Nworgu, Zuleikha A.M.,Falodun, Abiodun,Usifoh, Cyril O.
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p. 179 - 182
(2008/09/17)
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- Efficient carbonylation of aryl and heteroaryl bromides using a palladium/diadamantylbutylphosphine catalyst
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A general palladium-catalyzed alkoxycarbonylation of aryl and heteroaryl bromides has been developed in the presence of bulky monodentate phosphines. Studies of the butoxycarbonylation of three model substrates revealed the advantages of di-1-adamantyl-n-butylphosphine compared to other ligands. In the presence of this catalyst system various bromoarenes provided the corresponding benzoic acid derivatives (ester, amides, acids) in excellent yield at low catalyst loadings (0.5 mol% Pd or below).
- Neumann, Helfried,Brennfuehrer, Anne,Gross, Peter,Riermeier, Thomas,Almena, Juan,Beller, Matthias
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p. 1255 - 1261
(2007/10/03)
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- Development of new palladium catalysts for the alkoxycarbonylation of aryl chlorides
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The alkoxycarbonylation of different aryl chlorides was studied. Studies of the butoxycarbonylation of 4-chlorobenzotrifluoride and chlorobenzene using chelating ferrocenylphosphines reveal the advantages of these ligands compared to the well-known tricyc
- M?gerlein, Wolfgang,Indolese, Adriano F,Beller, Matthias
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- A more efficient catalyst for the carbonylation of chloroarenes
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The right ligand enables the efficient carbonylation of unactivated chloroarenes. A general synthesis of benzoic acid derivatives is possible with the palladium - Ferrocenylphosphane catalysts (see scheme).
- Maegerlein, Wolfgang,Indolese, Adriano F.,Beller, Matthias
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p. 2856 - 2859
(2007/10/03)
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- Efficient Palladium-Catalyzed Alkoxycarbonylation of N-Heteroaryl Chlorides - A Practical Synthesis of Building Blocks for Pharmaceuticals and Herbicides
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The alkoxycarbonylation of various N-heteroaryl chlorides was examined in detail. Studies of the butoxycarbonylation of 2- and 3-chloropyridine revealed the importance of selecting both the right phosphine ligand and ligand concentration in order to obtain efficient conversion and selectivity. Amongst the different ligands tested, 1,4-bis(diphenylphosphino)butane (dppb) and 1,1'-bis(diphenylphosphino)ferrocene (dppf) led to the most efficient palladium catalyst systems for the conversion of 2- and 4-chloropyridines and similar heteroaryl chlorides. The best catalytic systems for the alkoxycarbonylation of less activated substrates, such as 3-chloropyridines, were found to be those containing 1,4-bis(dicyclohexylphosphino)butane. Good to excellent yields of a number of N-heterocyclic carboxylic acid esters were realized by applying the appropriate ligand in the right concentration at low catalyst loadings (0.005-0.5 mol percent Pd). For the first time catalyst turnover numbers (TON) of up to 13,000 were obtained for the carbonylation of a (hetero)aryl chloride.
- Beller, Matthias,Maegerlein, Wolfganf,Indolese, Adriano F.,Fischer, Christine
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p. 1098 - 1109
(2007/10/03)
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