- Visible-Light-Enabled Carboxylation of Benzyl Alcohol Derivatives with CO2 Using a Palladium/Iridium Dual Catalyst
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A highly efficient carboxylation of benzyl alcohol derivatives with CO2 using a palladium/iridium dual catalyst under visible-light irradiation was developed. A wide range of benzyl alcohol derivatives could be employed to provide benzylic carboxylic acids in moderate to high yields. Mechanistic studies indicated that the oxidative addition of benzyl alcohol derivatives was possibly the rate-determining-step. It was also found that a switchable site-selective carboxylation between benzylic C?O and aryl C?Cl moieties could be achieved simply by changing the palladium catalyst.
- Iwasawa, Nobuharu,Jin, Yushu,Toriumi, Naoyuki
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- Desulfonylative Electrocarboxylation with Carbon Dioxide
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Electrocarboxylation of organic halides is one of the most investigated electrochemical approaches for converting thermodynamically inert carbon dioxide (CO2) into value-added carboxylic acids. By converting organic halides into their sulfone derivatives, we have developed a highly efficient electrochemical desulfonylative carboxylation protocol. Such a strategy takes advantage of CO2as the abundant C1 building block for the facile preparation of multifunctionalized carboxylic acids, including the nonsteroidal anti-inflammatory drug ibuprofen, under mild reaction conditions.
- Zhong, Jun-Song,Yang, Zi-Xin,Ding, Cheng-Lin,Huang, Ya-Feng,Zhao, Yi,Yan, Hong,Ye, Ke-Yin
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supporting information
p. 16162 - 16170
(2021/09/02)
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- Oxidation of Alkynyl Boronates to Carboxylic Acids, Esters, and Amides
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A general efficient protocol was developed for the synthesis of carboxylic acids, esters, and amides through oxidation of alkynyl boronates, generated directly from terminal alkynes. This protocol represents the first example of C(sp)?B bond oxidation. This approach displays a broad substrate scope, including aryl and alkyl alkynes, and exhibits excellent functional group tolerance. Water, primary and secondary alcohols, and amines are suitable nucleophiles for this transformation. Notably, amino acids and peptides can be used as nucleophiles, providing an efficient method for the synthesis and modification of peptides. The practicability of this methodology was further highlighted by the preparation of pharmaceutical molecules.
- Li, Chenchen,Li, Ruoling,Zhang, Bing,Zhao, Pei,Zhao, Wanxiang
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supporting information
p. 10913 - 10917
(2020/05/25)
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- Pd(OH)2/C, a Practical and Efficient Catalyst for the Carboxylation of Benzylic Bromides with Carbon Monoxide
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A simple, efficient, cheap, and broadly applicable system for the carboxylation of benzylic bromides with carbon monoxide and water is reported. Upon simple reaction with only 2.5 wt % of Pearlman's catalyst and 10 mol % of tetrabutylammonium bromide in tetrahydrofuran at 110 °C for 4 h, a range of benzylic bromides can be smoothly converted to the corresponding arylacetic acids in good to excellent yields after simple extraction and acid-base wash. The reaction was found to be broadly applicable, scalable, and could be successfully extended to the use of ex situ-generated carbon monoxide and applied to the synthesis of the nonsteroidal anti-inflammatory drug diclofenac.
- Wakuluk-Machado, Anne-Marie,Dewez, Damien F.,Baguia, Hajar,Imbratta, Miguel,Echeverria, Pierre-Georges,Evano, Gwilherm
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p. 713 - 723
(2020/02/04)
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- Electrogenerated Sm(II)-Catalyzed CO2 Activation for Carboxylation of Benzyl Halides
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Sm(II)-catalyzed carboxylation of benzyl halides is reported through the electrochemical reduction of CO2. The transformation proceeds under mild reaction conditions to afford the corresponding phenylacetic acids in good to excellent yields. This user-friendly and operationally simple protocol represents an alternative to traditional strategies, which usually proceeds through the C(sp3)-halide activation pathway.
- Bazzi, Sakna,Schulz, Emmanuelle,Mellah, Mohamed
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supporting information
p. 10033 - 10037
(2019/12/24)
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- Visible-Light-Driven External-Reductant-Free Cross-Electrophile Couplings of Tetraalkyl Ammonium Salts
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Cross-electrophile couplings between two electrophiles are powerful and economic methods to generate C-C bonds in the presence of stoichiometric external reductants. Herein, we report a novel strategy to realize the first external-reductant-free cross-electrophile coupling via visible-light photoredox catalysis. A variety of tetraalkyl ammonium salts, bearing primary, secondary, and tertiary C-N bonds, undergo selective couplings with aldehydes/ketone and CO2. Notably, the in situ generated byproduct, trimethylamine, is efficiently utilized as the electron donor. Moreover, this protocol exhibits mild reaction conditions, low catalyst loading, broad substrate scope, good functional group tolerance, and facile scalability. Mechanistic studies indicate that benzyl radicals and anions might be generated as the key intermediates via photocatalysis, providing a new direction for cross-electrophile couplings.
- Liao, Li-Li,Cao, Guang-Mei,Ye, Jian-Heng,Sun, Guo-Quan,Zhou, Wen-Jun,Gui, Yong-Yuan,Yan, Si-Shun,Shen, Guo,Yu, Da-Gang
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p. 17338 - 17342
(2019/01/04)
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- Synthetic method of fatty acid containing nitrogen heterocycle
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The invention discloses a synthetic method of fatty acid containing nitrogen heterocycle. The synthetic method comprises the following steps: (S1) adding a heterocyclic compound with substitution of chloromethyl groups, a catalyst and a solvent DMF into a reaction kettle; (S2) introducing carbon dioxide to lead the pressure in the kettle to be 2-4MPa, adjusting and reacting for 10-16 hours at thetemperature of 40-50 DEG C; (S3) adding diluted hydrochloric acid into the reaction kettle to carry out acidification, using ethyl acetate for extraction, combining organic phases, carrying out rotaryevaporation to remove liquid, and further carrying out vacuum drying, thus obtaining the fatty acid containing nitrogen heterocycle. The synthetic method disclosed by the invention has the beneficialeffects that a one-pot method is adopted, the raw materials are easy to obtain, price is low, aftertreatment of products is also simpler, the universality for a substrate is also very high, and the promotion and application are easy.
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Paragraph 0042
(2018/07/30)
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- Ruthenium-catalyzed umpolung carboxylation of hydrazones with CO2
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The first ruthenium-catalyzed umpolung carboxylation of hydrazones with CO2 to generate important aryl acetic acids is reported. Besides aldehyde hydrazones, a variety of ketone hydrazones, which have not been successfully applied in previous umpolung reactions with other reactive electrophiles, also show high reactivity and selectivity under mild conditions. Moreover, this operationally simple protocol features good functional group tolerance, is readily scalable, and offers easy derivation of important structures, including bioactive felbinac and adiphenine. Computational studies reveal that this umpolung reaction proceeds through the generation of a Ru-nitrenoid followed by concerted [4 + 2] cycloaddition with CO2.
- Yan, Si-Shun,Zhu, Lei,Ye, Jian-Heng,Zhang, Zhen,Huang, He,Zeng, Huiying,Li, Chao-Jun,Lan, Yu,Yu, Da-Gang
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p. 4873 - 4878
(2018/06/07)
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- A phenylacetic acid compound preparation method (by machine translation)
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The invention relates to the field of chemical synthesis, in particular relates to a preparation method of the compound of phenylacetic acid. The present invention provides a preparation method of the compound of phenylacetic acid, the acid compounds of the structural formula states the benzene second grade shown in formula I, the preparation method comprises the following steps: (1) diazo addition reaction: formula II compound containing vinylidene chloride, acid, diazotization reagent, phase transfer catalyst and a copper catalyst in the system of the formula III compound: (2) hydrolysis reaction: the compound of formula III in the presence of acid hydrolysis of formula I compounds. The present invention provides a preparation method of and is simple, easy operation, low cost of raw materials, mild reaction conditions, low risk, does not need to use expensive noble metal catalyst and complex industrial operation means, the product quality is stable, therefore easy achievement of large-scale industrial production. (by machine translation)
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Paragraph 0132
(2018/03/01)
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- Palladium-catalyzed silver-mediated α-arylation of acetic acid: A new approach for the α-arylation of carbonyl compounds
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A new approach for the α-arylation of acetic acid through Pd-catalyzed silver-mediated direct C-H arylation of acetic acid with aryl iodides was developed. This protocol provided a straightforward method for the synthesis of a diverse set of α-phenylacetic acids. Palladium served on a silver platter: A new approach for the α-arylation of acetic acid through Pd-catalyzed silver-mediated direct C-H arylation of acetic acid with aryl iodides is presented. This protocol provides a straightforward method for the synthesis of a diverse set of α-phenylacetic acids. Deuteration experiments are performed to help elucidate the reaction mechanism.
- Wu, Guo-Jie,Guan, Jing,Han, Fu-She,Zhao, Yu-Long
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p. 1589 - 1593
(2014/06/24)
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- Catalytic decarboxylative fluorination for the synthesis of Tri- and difluoromethyl arenes
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Treatment of readily available α,α-difluoro- and α-fluoroarylacetic acids with Selectfluor under Ag(I) catalysis led to decarboxylative fluorination. This operationally simple reaction gave access to tri- and difluoromethylarenes applying a late-stage fluorination strategy. Translation to [18F]labeling is demonstrated using [ 18F]Selectfluor bis(triflate), a reagent affording [ 18F]tri- and [18F]difluoromethylarenes not within reach with [18F]F2.
- Mizuta, Satoshi,Stenhagen, Ida S.R.,O'Duill, Miriam,Wolstenhulme, Jamie,Kirjavainen, Anna K.,Forsback, Sarita J.,Tredwell, Matthew,Sandford, Graham,Moore, Peter R.,Huiban, Mickael,Luthra, Sajinder K.,Passchier, Jan,Solin, Olof,Gouverneur, Véronique
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supporting information
p. 2648 - 2651
(2013/07/11)
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- Ni-catalyzed direct carboxylation of benzyl halides with CO2
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A novel Ni-catalyzed carboxylation of benzyl halides with CO2 has been developed. The described carboxylation reaction proceeds under mild conditions (atmospheric CO2 pressure) at room temperature. Unlike other routes for similar means, our method does not require well-defined and sensitive organometallic reagents and thus is a user-friendly and operationally simple protocol for assembling phenylacetic acids.
- León, Thierry,Correa, Arkaitz,Martin, Ruben
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supporting information
p. 1221 - 1224
(2013/03/14)
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- Pd-catalyzed deoxygenation of mandelate esters
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(Chemical Equation Presented) A new approach to the synthesis of phenylacetic acids and esters has been developed via the palladium-catalyzed deoxygenation of mandelate esters.
- Milne, Jacqueline E.,Murry, Jerry A.,King, Anthony,Larsen, Robert D.
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supporting information; experimental part
p. 445 - 447
(2009/04/10)
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- Electrocatalytic carboxylation of benzyl chlorides at silver cathodes in acetonitrile
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Silver exhibits powerful electrocatalytic activities towards the reductive carboxylation of benzyl chlorides (RCl): in CO2-saturated CH3CN, reduction of RCl occurs at potentials that are about 0.6 V more positive than those of the same process at Hg or carbon electrodes and gives carboxylic acids in good to excellent yields.
- Isse, Abdirisak A.,Gennaro, Armando
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p. 2798 - 2799
(2007/10/03)
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- An efficient method for one-carbon elongation of aryl aldehydes via their dibromoalkene derivatives
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Various aryl aldehydes were efficiently converted into one-carbon extended aryl acetamides or aryl acetic acids through the reaction of their dibromoalkene derivatives with pyrrolidine in the presence of water under very mild conditions.
- Huh, Dal Ho,Jeong, Ji Sang,Lee, Hee Bong,Ryu, Hoejin,Kim, Young Gyu
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p. 9925 - 9932
(2007/10/03)
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- Electrochemical carboxylation of arylmethyl chlorides catalysed by [Co(salen)] [H2salen = N,N′-bis(salicylidene)ethane-1,2-diamine]
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The electrochemical carboxylation of some arylmethyl chlorides RCl [R = benzyl, 4-methoxybenzyl, 4-(trifluoromethyl)benzyl or diphenylmethyl] catalysed by [Co(salen)] [H2salen = N,N′-bis(salicylidene)-ethane-1,2-diamine] was studied in acetonitrile. Comparable amounts of carboxylic acids and saturated hydrocarbons were obtained when R = PhCH2 or 4-MeOC6H4CH2 whereas carboxylic acids were the main products with R = 4-F3CC6H4CH2 or Ph2CH. Electrogenerated [Co1(salen)]- reacts with RCl to give an organometallic complex, [CoIII(salen)R], with a rate constant which, for all chlorides investigated, is of the order of 105 dm3 mol-1 s-1. The one-electron-reduced complex [CoII(salen)R]- is unstable and its decomposition in the presence of CO2 is the key step of the electrocatalytic process. Different decomposition pathways are considered and their mechanistic implications discussed. In the presence of proton donors [CoII(salen)R]- undergoes rapid hydrolysis to RH and [Co(salen)].
- Isse, Abdirisak Ahmed,Gennaro, Armando,Vianello, Elio
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p. 1613 - 1618
(2007/10/03)
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- Photolysis of the 1-naphthylmethyl ester of substituted phenylacetic acids: intramolecular charge transfer and rates of decarboxylation of arylacyl radicals
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The photolysis of esters 6 and 8 in methanol leads to products resulting from both naphthylmethyl cations and radicals.The product distribution is nearly independent of X for the esters 6 except when X equals methoxy.A mechanism involving initial homolytic cleavage of the carbon-oxygen bond in the excited singlet state of the ester is proposed.Competition between electron transfer in the radical pair to form the ion pair and decarboxylation of the arylacyloxy radical allows calculations of the rates of this decarboxylation process.The ρ values versus ? is close to zero.When X equals methoxy, intramolecular electron transfer occurs with the naphthalene ring serving as the acceptor and the methoxyaromatic as the donor.This exciplex fragments to carbon dioxide and 1-(1-naphthyl)-2-arylethane. Key words: acyloxy radical, decarboxylation, photolysis of benzylic esters.
- Hilborn, James W.,Pincock, James A.
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p. 992 - 999
(2007/10/02)
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- Degenerate Transesterification of 3,5-Dimethylphenolate/3,5-Dimethylphenyl Esters in Weakly Polar, Aprotic Solvents. Reactions of Aggregates and Complex-Induced Proximity Effects
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The rates of exchange of the 3,5-dimethylphenolate ion between lithium 3,5-dimethylphenolate-d6 and a series of 3,5-dimethylphenyl esters have been determined in the weakly polar, aprotic solvents dioxolane, dimethoxyethane (DME), tetrahydrofuran (THF), and pyridine. The esters include the propionate, butyrate, methoxyacctate, β-methoxypropionate, 4-methoxybutyrate, 2-tetrahydrofuroate, 2-furoate, (N,N-dimethylamino)acetate, (methylthio)acetate, 2- and 4-pyridine-carboxylates, 2-pyridylacetate, 4-pyridylacetate, phenylacetate, andp-methoxy-,p-chloro-, and p-(trifluoromethyl)phenylacetates. The rates and kinetic orders of the reactions of 3,5-dimethylphenyl propionate in various solvents at 35°C gave the following second-order rate constants (104k2, L mol-1 sec-1) for the following major aggregate species: THF tetramer, 6.5; DME tetramer, 3.3 (40°C); dioxolane, 13, hexamer, 71; pyridine tetramer, 2.2, dimer, 29. For 3,5-dimethylphenyl β-methoxypropionate, the order of reactivity is dioxolane > DME > THF. These results are interpreted in terms of a preequilibrium in which a solvent on lithium in the tetramer is replaced by the ester. The rates of transesterification have been compared with the rates of hydrolysis in 30% aqueous ethanol for the above series of esters. Those esters that have a second Lewis base center proximal to the ester function show significantly increased reactivity in transesterification, which is attributed to a complex-induced proximity effect.
- Jackman,Petrei,Smith
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p. 3451 - 3458
(2007/10/02)
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- Micellar Catalysis of the Basic Hydrolysis of Anilides. III α-Substituted N-Methyl-N-p-nitrophenylacetamides
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The basic hydrolysis of a number of α-substituted N-methyl-N-p-nitrophenylacetamides has been studied both in the presence and absence of micelles of cetyltrimethylammonium bromide (ctab).Unlike the related p-nitrophenyl esters of α-substituted acetic acids, no evidence for the operation of the E1cb mechanism in the basic hydrolysis has been detected.Reasons for the differences between the amides and esters are discussed.Substituent effects on the hydrolysis of the amides have been studied both by single-parameter and dual-parameter analysis.
- Broxton, Trevor J.,Duddy, Neil W.
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p. 1771 - 1781
(2007/10/02)
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