- Exploiting a silver-bismuth hybrid material as heterogeneous noble metal catalyst for decarboxylations and decarboxylative deuterations of carboxylic acids under batch and continuous flow conditions
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Herein, we report novel catalytic methodologies for protodecarboxylations and decarboxylative deuterations of carboxylic acids utilizing a silver-containing hybrid material as a heterogeneous noble metal catalyst. After an initial batch method development, a chemically intensified continuous flow process was established in a simple packed-bed system which enabled gram-scale protodecarboxlyations without detectable structural degradation of the catalyst. The scope and applicability of the batch and flow processes were demonstrated through decarboxylations of a diverse set of aromatic carboxylic acids. Catalytic decarboxylative deuterations were achieved on the basis of the reaction conditions developed for the protodecarboxylations using D2O as a readily available deuterium source.
- ?tv?s, Sándor B.,Fül?p, Ferenc,Kónya, Zoltán,Kukovecz, ákos,Márton, András,Mészáros, Rebeka,Pálinkó, István,Szabados, Márton,Varga, Gábor
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p. 4685 - 4696
(2021/07/12)
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- A Predictive Model for the Decarboxylation of Silver Benzoate Complexes Relevant to Decarboxylative Coupling Reactions
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Decarboxylative coupling reactions offer an attractive route to generate functionalized arenes from simple and readily available carboxylic acid coupling partners, yet they are underutilized due to limitations in the scope of carboxylic acid coupling partner. Here we report that the field effect parameter (F) has a substantial influence on the rate of decarboxylation of well-defined silver benzoate complexes. This finding provides the opportunity to surpass current substrate limitations associated with decarboxylation and to enable widespread utilization of decarboxylative coupling reactions.
- Crovak, Robert A.,Hoover, Jessica M.
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supporting information
p. 2434 - 2437
(2018/02/28)
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- Method for synthesizing 3,4-difluoro-2'-aminobiphenyl
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The invention relates to a method for synthesizing 3,4-difluoro-2'-aminobiphenyl. The method comprises: carrying out a reaction on o-nitrobenzoic acid, an alkali and a solvent, removing the water, adding substituted halobenzene, a catalyst and a ligand, c
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Paragraph 0089; 0090; 0102; 0103
(2018/03/28)
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- o-aminobiphenyl compound synthesis method
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The invention relates to an o-aminobiphenyl compound synthesis method, which comprises: carrying out a reaction on an o-nitroaromatic formic acid compound, an alkali and a solvent, removing water, adding substituted halobenzene, a catalyst and a ligand, carrying out a reaction, or carrying out a reaction on a pre-prepared o-nitroaromatic formate, substituted halobenzene, a catalyst, a ligand and a solvent, and carrying out post-treatment to obtain the o-aminobiphenyl compound. According to the present invention, the o-aminobiphenyl compound is synthesized by using the easily available or easily prepared o-nitroaromatic formate and the substituted halobenzene as the raw material through the one-step method without the use of hydrogen and other hazardous reducing agents, such that the coupling and nitro reduction continuous reaction is achieved, and the advantages of new reaction, safety, high efficiency, simple operation and low cost are provided.
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Paragraph 0082; 0083; 0084
(2018/04/02)
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- Arylalkene synthesis via decarboxylative cross-coupling of alkenyl halides
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A bimetallic catalyst system generated from readily available palladium(II) and copper(I) salts, 1,10-phenanthroline and tri-1-naphthylphosphine was found to efficiently mediate the decarboxylative cross-coupling of alkenyl bromides and chlorides with aromatic carboxylates. It allows the regiospecific synthesis of a broad range of aryl- and heteroarylalkenes in high yields.
- Tang, Jie,Goossen, Lukas J.
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supporting information
p. 2664 - 2667
(2014/06/09)
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- Decarboxylative cross-coupling of mesylates catalyzed by copper/palladium systems with customized imidazolyl phosphine ligands
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The activation of the inert C-O bonds in mesylates through the use of a new class of imidazolyl phosphines allows the decarboxylative coupling of aryl mesylates as well as polysubstituted alkenyl mesylates. Variation of the ligands leads to two complementary methods providing the corresponding biaryls and polysubstituted olefins in good yields. Copyright
- Song, Bingrui,Knauber, Thomas,Goo?en, Lukas J.
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supporting information
p. 2954 - 2958
(2013/04/11)
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- Decarboxylative etherification of aromatic carboxylic acids
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Decarboxylative Chan-Evans-Lam-type couplings are presented as a new strategy for the regiospecific construction of diaryl and alkyl aryl ethers starting from easily available aromatic carboxylic acids. They allow converting various aromatic carboxylate salts into the corresponding aryl ethers by reaction with alkyl orthosilicates or aryl borates, under aerobic conditions in the presence of silver carbonate as the decarboxylation catalyst and copper acetate as the cross-coupling catalyst.
- Bhadra, Sukalyan,Dzik, Wojciech I.,Goossen, Lukas J.
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supporting information; experimental part
p. 9938 - 9941
(2012/08/08)
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- Low-Temperature Ag/Pd-catalyzed decarboxylative cross-coupling of aryl trflates with aromatic carboxylate salts
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Chemical Equation Presented At 50°C lower than the best known copper catalysts, a catalytic silver(I)/ palladium(II) system allows the decarboxylative cross-coupling of arenecarboxylates with aryl triflates at temper-atures as low as 120°C. Remarkably, polychlorinated and many heterocyclic arenecarboxylates are converted for the first time in high yields. FG = functional group.
- Goossen, Lukas J.,Lange, Paul P.,Rodriguez, Nuria,Linder, Christophe
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supporting information; experimental part
p. 3906 - 3909
(2010/07/03)
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- Decarboxylative cross-coupling of aryl tosylates with aromatic carboxylate salts
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(Figure Presented) A bimetallic copper/palladium catalyst system is disclosed that enables the use of tosylates as carbon electrophiles in decarboxylative coupling reactions. A variety of aromatic carboxylate salts, regardless of their substitution pattern, have been coupled with these inexpensive and readily available electrophiles to give the corresponding biaryl compounds in good yields (see scheme).
- Goossen, Luksa J.,Rodriguez, Nuria,Lange, Paul P.,Linder, Christophe
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supporting information; experimental part
p. 1111 - 1114
(2010/04/29)
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- Pd-catalyzed decarboxylative Heck vinylation of 2-nitrobenzoates in the presence of CuF2
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A new protocol for the decarboxylative Heck vinylation of benzoic acids is disclosed. In the presence of a catalyst system generated in situ from Pd(OAc)2 (2 mol %), CuF2 (2 equiv), and benzoquinone (0.5 equiv) in NMP, a wide range of olefins were coupled with various 2-nitrobenzoates at 130 °C with the release of carbon dioxide to afford the corresponding vinyl arenes in good yields.
- Goossen, Lukas J.,Zimmermann, Bettina,Knauber, Thomas
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supporting information; experimental part
(2010/08/19)
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- Biaryl and aryl ketone synthesis via Pd-catalyzed decarboxylase coupling of carboxylate salts with aryl triflates
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A bimetallic catalyst system has been developed that for the first time allows the decarboxylative crosscoupling of aryl and acyl carboxylates with aryl triflates. In contrast to aryl halides, these electrophiles give rise to non-coordinating anions as byproducts, which do not interfere with the decarboxylation step that leads to the generation of the carbon nucleophilic crosscoupling partner. As a result, the scope of carboxylate substrates usable in this transformation was extended from ortho-substituted or otherwise activated derivatives to a broad range of ortho-, meta-, and para-substituted aromatic carboxylates. Two alternative protocols have been optimized, one involving heating the substrates in the presence of CuI/1,10- phenanthroline (10-15 mol %) and PdI2/phosphine (23 mol%) in NMP for 1-24 h, the other involving CuI/l,10-phenanthroline (615mol%) and PdBr2/Tol-BINAP (2 mol % ) in NMP using microwave heating for 5-10 min. While most products are accessible using standard heating, the use of microwave irradiation was found to be beneficial especially for the conversion of non-activated carboxylates with functionalized aryl triflates. The synthetic utility of the transformation is demonstrated with 48 examples showing the scope and limitations of both protocols. In mechanistic studies, the special role of microwave irradiation is elucidated, and further perspectives of decarboxylase crosscouplings are discussed.
- Goossen, Lukas J.,Linder, Christophe,Rodriguez, Nuria,Lange, Paul P.
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supporting information; experimental part
p. 9336 - 9349
(2010/04/03)
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- Synthesis of biaryls and aryl ketones via microwave-assisted decarboxylative cross-couplings
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A protocol for the microwave-assisted decarboxylative cross-couplings of carboxylic acid salts with aryl halides has been developed that allows the synthesis of various biaryls and aryl ketones in high yields. After careful adaptation of the bimetallic ca
- Goossen, Lukas J.,Linder, Bettina Zimmermanns Christophe,Rodriguez, Nuria,Lange, Paul P.,Hartung, Jens
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experimental part
p. 2667 - 2674
(2009/12/31)
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- Decarboxylative biaryl synthesis from aromatic carboxylates and aryl triflates
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A new catalyst system, generated in situ from Cu2O, 1,10-phenanthroline, PdI2, and Tol-BINAP, for the first time allows the decarboxylative coupling of carboxylic acids with aryl triflates. In contrast to previous decarboxylative couplings that remained limited to certain activated carboxylates, e.g., ortho-substituted benzoates, this halide-free protocol is generally applicable to aromatic carboxylic acid salts regardless of their substitution pattern. Copyright
- Goossen, Lukas J.,Rodriguez, Nuria,Linder, Christophe
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supporting information; experimental part
p. 15248 - 15249
(2009/03/11)
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- Method For Decarboxylating C-C Cross-Linking Of Carboxylic Acids With Carbon Electrophiles
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The invention relates to a method for decarboxylating C—C bond formation by reacting carboxylic salts with carbon electrophiles in the presence of transition metal compounds as catalysts. The method represents a decarboxylating C—C bond formation of carboxylic acid salts with carbon electrophiles, wherein the catalyst contains two transition metals and/or transition metal compounds, from which one is present, preferably, in the oxidation step, which are different from each other by one unit, and catalyzes a radical decarboxylation which is absorbed during the second oxidation steps, which are different from each other by two units and catalyzes the two electron processes of a C—C bond formation reaction.
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Page/Page column 4
(2008/12/07)
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