- Potential proinsecticides of fluorinated carboxylic acids and β-ethanolamines. IV. Evaluation of the Δ2-oxazoline-1,3 structure by 19F NMR monitoring of the in vitro metabolism in locust tissues
-
The enzymatic effect of locust tissues upon hydrolysis of the fluorinated Δ2-oxazoline-1,3 Ia was elucidated using 19F[1H] NMR monitoring. In a phosphate buffer at pH = 7.4 (mean physiological pH of locust tissues), the substrate Ia hydrolyses slowly into the corresponding fluorinated hydroxylamide VIa. If diluted, locust haemolymph (12.5% in phosphate buffer) catalyses slightly this hydrolytic pathway, it overall triggers the unmasking of carboxylate IIIa, corresponding to the expected proinsecticide behaviour of Ia. This behaviour is spectacularly almost the unique reaction observed during in vitro assays in concentrated fat body and mesenteron. Inasmuch as β-hydroxylamide VIa is not hydrolysed into carboxylate IIIa during such conditions, it must be concluded that carboxylate formation exclusively results from hydration and hydrolysis of substrate Ia via the aminoester Va. The formation of this intermediate aminoester is demonstrated by complementary assays. The enzymes supposed to intervene are of the α-chymotrypsine type for the first step (hydration) and of the esterase type for subsequent hydrolysis of intermediate aminoester Va. Thus, this work constitutes the first example of a Δ2-oxazoline-1,3 structure exploited for elaborating proinsecticides of carboxylates III and/or β-ethanolamines II based on enzymatic activation in insects.
- Cherton,Hamm,Halle,Menguy,Beaufour
-
-
Read Online
- Visible-Light-Enabled Carboxylation of Benzyl Alcohol Derivatives with CO2 Using a Palladium/Iridium Dual Catalyst
-
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
-
-
- Desulfonylative Electrocarboxylation with Carbon Dioxide
-
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
-
supporting information
p. 16162 - 16170
(2021/09/02)
-
- Oxidation of Alkynyl Boronates to Carboxylic Acids, Esters, and Amides
-
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
-
supporting information
p. 10913 - 10917
(2020/05/25)
-
- Method for converting benzyl borate compounds into phenylacetic acid and derivatives thereof by carbon dioxide
-
The invention discloses a method for converting benzyl borate compounds into phenylacetic acid and derivatives thereof by carbon dioxide. The method comprises the steps: dissolving the benzyl borate compounds and an alkali in an organic solvent in the absence of a metal catalyst, introducing carbon dioxide into the reaction system, carrying out a reaction at the temperature of 50-150 DEG C for 3-72 hours, and acidifying to obtain phenylacetic acid or the derivatives thereof. The method is a green, simple and efficient method for synthesizing phenylacetic acid and the derivatives thereof, greenhouse gas carbon dioxide is used as a carbon source in the reaction, no transition metal catalyst is used, and the method is environmentally friendly, economical and high in efficiency.
- -
-
Paragraph 0034-0035
(2020/03/06)
-
- BF3·OEt2-promoted tandem Meinwald rearrangement and nucleophilic substitution of oxiranecarbonitriles
-
Tandem Meinwald rearrangement and nucleophilic substitution of oxiranenitriles was realized. Arylacetic acid derivatives were readily synthesized from 3-aryloxirane-2-carbonitriles with amines, alcohols, or water in the presence of boron trifluoride under microwave irradiation, and the designed synthetic strategy includes introducing a cyano leaving group into arylepoxides and capturing the in situ generated toxic cyanide with boron trifluoride, making the reaction efficient, safe, and environmentally benign. The reaction occurs through an acid-promoted Meinwald rearrangement, producing arylacetyl cyanides, followed by an addition-elimination process with nitrogen or oxygen-containing nucleophilic amines, alcohols or water. The current method provides a new application of the tandem Meinwald rearrangement.
- Xu, Chuangchuang,Xu, Jiaxi
-
p. 127 - 134
(2019/12/26)
-
- Pd(OH)2/C, a Practical and Efficient Catalyst for the Carboxylation of Benzylic Bromides with Carbon Monoxide
-
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
-
p. 713 - 723
(2020/02/04)
-
- Preparation method of phenylacetic acid type compound
-
The invention discloses a preparation method of a phenylacetic acid type compound. The preparation method of the phenylacetic acid type compound I comprises the following steps that in a solvent and aCO gas phase system, a benzyl halide type compound II, pyridine-2-cobalt carboxylate, palladium acetate and alkaline neutralizers take carbonylation reaction to obtain the phenylacetic acid type compound I. A mixed catalytic system has a synergistic effect; the whole use quantity of catalysts is greatly reduced. When the mixed catalyst is used, a better catalytic effect can be achieved; the characteristics of easily obtaining the catalyst, avoiding the production safety risk of toxic three wastes and the like, reducing the reaction pressure, realizing mild reaction conditions, reducing the production risk, facilitating the production and the like are realized. The formulas are shown in description.
- -
-
Paragraph 0054; 0055; 0056
(2019/02/21)
-
- An improved method for the synthesis of phenylacetic acid derivatives via carbonylation
-
2,4-Dichlorophenylacetic acid is synthesized in high yield via the carbonylation of 2,4-dichlorobenzyl chloride, and various experimental conditions are evaluated. Xylene, bistriphenylphosphine palladium dichloride, tetraethylammonium chloride and sodium hydroxide in solution are added to the reaction system and held at 80 °C under a CO atmosphere. 2,4-Dichlorophenylacetic acid is obtained in a maximum yield of 95percent, and a mechanism for 2,4-dichlorobenzyl chloride carbonylation is proposed. The reaction system provides a mild, effective and novel means by which to prepare phenylacetic acid derivatives from their corresponding benzyl chloride derivatives.
- Li, He,Zhang, Yijun,Liu, Dinghua,Liu, Xiaoqin
-
p. 548 - 552
(2019/11/13)
-
- Electrogenerated Sm(II)-Catalyzed CO2 Activation for Carboxylation of Benzyl Halides
-
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
-
supporting information
p. 10033 - 10037
(2019/12/24)
-
- Synthesis and biological evaluation of 3-arylcoumarin derivatives as potential anti-diabetic agents
-
A variety of substituted 3-arylcoumarin derivatives were synthesised through microwave radiation heating. The method has characteristics of environmental friendliness, economy, simple separation, and purification process, less by-products and high reaction yield. Those 3-arylcoumarin derivatives were screened for antioxidant, α-glucosidase inhibitory and advanced glycation end-products (AGEs) formation inhibitory. Most compounds exhibited significant antioxidant and AGEs formation inhibitory activities. Anti-diabetic activity studies showed that compounds 11 and 17 were equipotent to the standard drug glibenclamide in vivo. According to the experimental results, the target compound 35 can be used as a lead compound for the development of new anti-diabetic drugs. The whole experiment showed that anti-diabetic activity is prevalent in 3-arylcoumarins, which added a new natural skeleton to the development of anti-diabetic active drugs.
- Hu, Yuheng,Wang, Bing,Yang, Jie,Liu, Teng,Sun, Jie,Wang, Xiaojing
-
-
- Synthesis and biological evaluation of 3-arylcoumarins as potential anti-Alzheimer's disease agents
-
Alzheimer's disease, a neurodegenerative illness, has the extremely complex pathogenesis. Accumulating evidence indicates there is a close relationship between several enzymes and Alzheimer's disease. Various substituted 3-arylcoumarin derivatives were synthesised, and their in vitro activity, including cholinesterase inhibitory activity, monoamine oxidase inhibitory activity, and antioxidant activity were investigated. Most of the compounds exhibited high activity; therefore 3-arylcoumarin compounds have the potential as drug candidates for the treatment of Alzheimer's disease.
- Yang, Jie,Zhang, Pingping,Hu, Yuheng,Liu, Teng,Sun, Jie,Wang, Xiaojing
-
p. 651 - 656
(2019/02/19)
-
- Preparation method of acid with different substituent groups
-
The invention discloses a preparation method of an acid with different substituent groups. A terminal alkyne is lithiated with n-butyllithium, and then reacts with isopropoxyboronic acid pinacol ester, hydrogen chloride is added to achieve quenching, then the obtained reaction product is oxidized by an oxidizing agent, and the oxidized reaction product is separated and purified to obtain the acid.The method of the invention has the advantages of simplicity in operation, one-pot process preparation, no metal catalysis, nontoxic reagents, greenness, environmental friendliness and high atomic utilization rate, and provides a novel and quick way for preparing the acid with different substituent groups; and the obtained acid is an important fine chemical product, and can be widely used in fields of medicines, pesticides, spices and other industries.
- -
-
Paragraph 0118-0123
(2019/10/23)
-
- Carboxylation of benzylic and aliphatic C-H bonds with CO2 induced by light/ketone/nickel
-
A photoinduced carboxylation reaction of benzylic and aliphatic C-H bonds with CO2 is developed. Toluene derivatives capture gaseous CO2 at the benzylic position to produce phenylacetic acid derivatives when irradiated with UV light in the presence of an aromatic ketone, a nickel complex, and potassium tert-butoxide. Cyclohexane reacts with CO2 to furnish cyclohexanecar-boxylic acid under analogous reaction conditions. The present photoinduced carboxylation reaction provides a direct access from readily available hydrocarbons to the corresponding carboxylic acids with one carbon extension.
- Ishida, Naoki,Masuda, Yusuke,Imamura, Yuuya,Yamazaki, Katsushi,Murakami, Masahiro
-
supporting information
p. 19611 - 19615
(2019/12/24)
-
- Design and evolution of an enzyme with a non-canonical organocatalytic mechanism
-
The combination of computational design and laboratory evolution is a powerful and potentially versatile strategy for the development of enzymes with new functions1–4. However, the limited functionality presented by the genetic code restricts the range of catalytic mechanisms that are accessible in designed active sites. Inspired by mechanistic strategies from small-molecule organocatalysis5, here we report the generation of a hydrolytic enzyme that uses Nδ-methylhistidine as a non-canonical catalytic nucleophile. Histidine methylation is essential for catalytic function because it prevents the formation of unreactive acyl-enzyme intermediates, which has been a long-standing challenge when using canonical nucleophiles in enzyme design6–10. Enzyme performance was optimized using directed evolution protocols adapted to an expanded genetic code, affording a biocatalyst capable of accelerating ester hydrolysis with greater than 9,000-fold increased efficiency over free Nδ-methylhistidine in solution. Crystallographic snapshots along the evolutionary trajectory highlight the catalytic devices that are responsible for this increase in efficiency. Nδ-methylhistidine can be considered to be a genetically encodable surrogate of the widely employed nucleophilic catalyst dimethylaminopyridine11, and its use will create opportunities to design and engineer enzymes for a wealth of valuable chemical transformations.
- Burke, Ashleigh J.,Lovelock, Sarah L.,Frese, Amina,Crawshaw, Rebecca,Ortmayer, Mary,Dunstan, Mark,Levy, Colin,Green, Anthony P.
-
p. 219 - 223
(2019/06/13)
-
- Synthetic method of fatty acid containing nitrogen heterocycle
-
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.
- -
-
Paragraph 0042
(2018/07/30)
-
- Visible-Light-Driven External-Reductant-Free Cross-Electrophile Couplings of Tetraalkyl Ammonium Salts
-
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
-
p. 17338 - 17342
(2019/01/04)
-
- A General, Activator-Free Palladium-Catalyzed Synthesis of Arylacetic and Benzoic Acids from Formic Acid
-
A new catalyst for the carboxylative synthesis of arylacetic and benzoic acids using formic acid (HCOOH) as the CO surrogate was developed. In an improvement over previous work, CO is generated in situ without the need for any additional activators. Key to success was the use of a specific system consisting of palladium acetate and 1,2-bis((tert-butyl(2-pyridinyl)phosphinyl)methyl)benzene. The generality of this method is demonstrated by the synthesis of more than 30 carboxylic acids, including non-steroidal anti-inflammatory drugs (NSAIDs), under mild conditions in good yields.
- Wang, Lin,Neumann, Helfried,Beller, Matthias
-
supporting information
p. 6910 - 6914
(2018/06/04)
-
- Ruthenium-catalyzed umpolung carboxylation of hydrazones with CO2
-
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
-
p. 4873 - 4878
(2018/06/07)
-
- Diphenylurea derivatives for combating methicillin- and vancomycin-resistant Staphylococcus aureus
-
A new class of diphenylurea was identified as a novel antibacterial scaffold with an antibacterial spectrum that includes highly resistant staphylococcal isolates, namely methicillin- and vancomycin-resistant Staphylococcus aureus (MRSA & VRSA). Starting with a lead compound 3 that carries an aminoguanidine functionality from one side and a n-butyl moiety on the other ring, several analogues were prepared. Considering the pharmacokinetic parameters as a key factor in structural optimization, the structure-activity-relationships (SARs) at the lipophilic side chain were rigorously examined leading to the discovery of the cycloheptyloxyl analogue 21n as a potential drug-candidate. This compound has several notable advantages over vancomycin and linezolid including rapid killing kinetics against MRSA and the ability to target and reduce the burden of MRSA harboring inside immune cells (macrophages). Furthermore, the potent anti-MRSA activity of 21n was confirmed in?vivo using a Caenorhabditis elegans animal model. The present study provides a foundation for further development of diphenylurea compounds as potential therapeutic agents to address the burgeoning challenge of bacterial resistance to antibiotics.
- Eissa, Ibrahim H.,Mohammad, Haroon,Qassem, Omar A.,Younis, Waleed,Abdelghany, Tamer M.,Elshafeey, Ahmed,Abd Rabo Moustafa, Mahmoud M.,Seleem, Mohamed N.,Mayhoub, Abdelrahman S.
-
supporting information
p. 73 - 85
(2017/03/02)
-
- Preparation method of fluorophenylacetic acid
-
The invention relates to the field of chemical synthesis, and particularly relates to a preparation method of fluorophenylacetic acid. The invention provides a preparation method of fluorophenylacetic acid. The preparation method comprises the following steps: diazotization addition reaction: enabling a compound of the formula II to react in a system containing vinylidene chloride, acid, a diazonino reagent, a phase transfer catalyst and a copper catalyst to produce a compound of the formula III; and hydrolysis reaction: hydrolyzing the compound of the formula III to produce a compound of the formula I under the existence condition of acid. The preparation method is simply and easily available in raw materials, simple and convenient to operate, low in raw material cost, mild in reaction conditions, and low in danger, free from the use of high-price noble metal catalyst and complicated industrial operation means, and the quality of the product is stable, and therefore, the preparation method is suitable for industrial large-scale production.
- -
-
Paragraph 0086; 0087; 0089
(2017/08/24)
-
- Regio- and Stereoselective Oxidation of Styrene Derivatives to Arylalkanoic Acids via One-Pot Cascade Biotransformations
-
Green and selective oxidation methods are highly desired in chemical synthesis and manufacturing. In this work, we have developed a biocatalytic method for the regio- and stereoselective oxidation of styrene derivatives into arylacetic and (S)-2-arylpropionic acids via a one-pot epoxidation–isomerization–oxidation sequence. This was done via the engineering of Escherichia coli (StyABC-EcALDH) coexpressing styrene monooxygenase (SMO), styrene oxide isomerase (SOI) and aldehyde dehydrogenase (EcALDH) as an active and easily available whole-cell catalyst. Regioselective oxidation of styrene and 11 substituted styrenes using the E. coli cells was performed in a one-pot set-up, producing 12 phenylacetic acids in both high conversion and high yield. Engineering of E. coli (StyABC-ADH9v1) coexpressing SMO, SOI and ADH9v1 (a mutated alcohol dehydrogenase) led to biocatalysts capable of regio- and stereoselective oxidation of α-methylstyrene derivatives to the corresponding chiral acids. One-pot asymmetric synthesis of 4 (S)-2-arylpropionic acids was achieved in good conversion and excellent ee with the E. coli cells. This is a new type of asymmetric alkene oxidation to give chiral acids with no chemical counterpart thus far. The cascade bio-oxidation operates under mild conditions, uses molecular oxygen, exhibits very high regio- and enantioselectivity, and gives high conversion, thus providing a green and efficient method for the synthesis of arylacetic acids and (S)-2-arylpropionic acids directly from easily available styrenes. (Figure presented.).
- Wu, Shuke,Zhou, Yi,Seet, Daniel,Li, Zhi
-
p. 2132 - 2141
(2017/06/23)
-
- Nickel-Catalyzed Carboxylation of Benzylic C-N Bonds with CO2
-
A user-friendly Ni-catalyzed reductive carboxylation of benzylic C-N bonds with CO2 is described. This procedure outperforms state-of-the-art techniques for the carboxylation of benzyl electrophiles by avoiding commonly observed parasitic pathways, such as homodimerization or β-hydride elimination, thus leading to new knowledge in cross-electrophile reactions.
- Moragas, Toni,Gaydou, Morgane,Martin, Ruben
-
supporting information
p. 5053 - 5057
(2016/04/26)
-
- Metal-free, catalytic regioselective oxidative conversion of vinylarenes: A mild approach to phenylacetic acid derivatives
-
A new synthetic approach towards the synthesis of phenylacetic acids from aromatic alkenes has been developed for the first time under mild conditions by employing non-toxic reagents such as molecular iodine and oxone. This metal-free catalytic regioselective oxygenation of vinylarenes proceeds via tandem iodofunctionalization/de-iodination induced rearrangement.
- Kodumuri, Srujana,Peraka, Swamy,Mameda, Naresh,Chevella, Durgaiah,Banothu, Rammurthy,Nama, Narender
-
p. 6719 - 6723
(2016/02/03)
-
- Palladium-catalyzed silver-mediated α-arylation of acetic acid: A new approach for the α-arylation of carbonyl compounds
-
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
-
p. 1589 - 1593
(2014/06/24)
-
- PROCESS FOR SYNTHESIZING PHENYLACETIC ACID BY CARBONYLATION OF TOLUENE
-
A production process for substituted phenylacetic acids or ester analogues thereof is disclosed. In this process toluene or toluene substituted with various substituents, an alcohol, an oxidant and carbon monoxide are used as raw materials to obtain compounds comprising structure of phenylacetic acid ester or analogues thereof by catalysis of the complex catalyst formed from transition metal and ligand, and such compounds are hydrolyzed to obtain various substituted phenylacetic acid based compounds. This type of compounds and their derivatives serve as important fine chemicals used widely in the industries of pharmaceuticals, pesticides, perfume and the like.
- -
-
Paragraph 0018; 0060; 0061
(2013/11/19)
-
- Palladium(III)-catalyzed fluorination of arylboronic acid derivatives
-
A practical, palladium-catalyzed synthesis of aryl fluorides from arylboronic acid derivatives is presented. The reaction is operationally simple and amenable to multigram-scale synthesis. Evaluation of the reaction mechanism suggests a single-electron-transfer pathway, involving a Pd(III) intermediate that has been isolated and characterized.
- Mazzotti, Anthony R.,Campbell, Michael G.,Tang, Pingping,Murphy, Jennifer M.,Ritter, Tobias
-
supporting information
p. 14012 - 14015
(2013/10/21)
-
- An efficiently cobalt-catalyzed carbonylative approach to phenylacetic acid derivatives
-
A highly efficient cobalt-catalyzed carbonylative approach to phenylacetic acid derivatives under one atmosphere pressure is reported. This methodology represents a useful extension of benzimidazole used as ligand in metal catalysis, and the catalytic mechanism has been proved by computer simulation. Notably, this new cobalt precatalyst, which promotes the carbonylation reaction dramatically and has already been used for scale-up experiment of phenylacetic acid derivatives.
- She, Meng-Yao,Xiao, Da-Wei,Yin, Bing,Yang, Zheng,Liu, Ping,Li, Jian-Li,Shi, Zhen
-
p. 7264 - 7268
(2013/08/23)
-
- Ni-catalyzed direct carboxylation of benzyl halides with CO2
-
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
-
supporting information
p. 1221 - 1224
(2013/03/14)
-
- Development of a one-pot method for the homologation of aldehydes to carboxylic acids
-
A highly efficient method is described for the one-carbon homologation of aldehydes to carboxylic acid derivatives employing the reaction of a 1,1-bis-dimethylphosphonate derivative with the aldehyde and controlled acid hydrolysis of the derived α-phosphonoenamine intermediate.
- McNulty, James,Das, Priyabrata
-
experimental part
p. 7794 - 7800
(2009/12/26)
-
- Pd-catalyzed deoxygenation of mandelate esters
-
(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.
-
supporting information; experimental part
p. 445 - 447
(2009/04/10)
-
- PROCESS FOR THE PREPARATION OF FLUOROPHENYLACETIC ACIDS AND DERIVATIVES THEREOF
-
The object of the present invention is a process for the preparation of fluorophenylacetic acids and derivatives thereof, particularly of 2,4, 5-trifluorophenylacetic acid, starting from the corresponding mandelic acids.
- -
-
Page/Page column 23-24
(2008/12/06)
-
- SULFURIC ACID MONO-[3-({1-[2-(4-FLUORO-PHENYL)-ETHYL]-PIPERIDIN-4-YL}-HYDROXY-METHYL)-2-METHOXY-PHENYL]ESTER
-
The present invention is directed to sulfuric acid mono-[3-({1-[2-(4-fluoro-phenyl)-ethyl]-piperidin-4-yl}-hydroxy-methyl)-2-methoxy-phenyl]ester a metabolite of the 5HT2A antagonist (+)- alpha -(2,3-dimethoxyphenyl)-1-[2-(4-fluorophenyl)ethyl]-4-piperidinemethanol and a processes for its preparation and its use in the treatment for a number of disease states.
- -
-
Page/Page column 12
(2010/11/25)
-
- A novel method for synthesis of arylacetic acids from aldehydes, N-(2,3,4,6-tetra-O-pivaloylated-D-glucopyranosyl)amine and trimethylsilylcyanide
-
A novel synthetic approach for the preparation of arylacetic acids via the reaction of aldehydes, N-(2,3,4,6-tetra-O-pivaloylated-D-glucopyranosyl)amine and trimethylsilylcyanide was developed, in which the N-(2,3,4,6-tetra-O- pivaloylated-D-glucopyranosyl)amine can be recycled conveniently and reused efficiently.
- Zhou, Guo-Bin,Zhang, Peng-Fei,Pan, Yuan-Jiang
-
p. 5671 - 5677
(2007/10/03)
-
- Heterocyclic analgesic compounds and methods of use thereof
-
One aspect of the present invention relates to novel heterocyclic compounds. A second aspect of the present invention relates to the use of the novel heterocyclic compounds as ligands for various cellular receptors, including opiate receptors, other G-protein-coupled receptors, and ion channels. An additional aspect of the present invention relates to the use of the novel heterocyclic compounds as analgesics.
- -
-
-
- Heterocyclic analgesic compounds and methods of use thereof
-
One aspect of the present invention relates to novel heterocyclic compounds. A second aspect of the present invention relates to the use of the novel heterocyclic compounds as ligands for various cellular receptors, including opiate receptors, other G-protein-coupled receptors, and ion channels. An additional aspect of the present invention relates to the use of the novel heterocyclic compounds as analgesics.
- -
-
-
- Heterocyclic analgesic compounds and methods of use thereof
-
One aspect of the present invention relates to novel heterocyclic compounds. A second aspect of the present invention relates to the use of the novel heterocyclic compounds as ligands for various cellular receptors, including opiate receptors, other G-protein-coupled receptors, and ion channels. An additional aspect of the present invention relates to the use of the novel heterocyclic compounds as analgesics.
- -
-
-
- Catalytic carbonylation of benzylic and allylic bromides by a rhodium zwitterionic complex under phase transfer catalysis conditions
-
The zwitterionic rhodium complex, (COD)Rh(η6-C6H5BPh3) (1), can catalyze the carbonylation of benzylic and allylic bromides in the presence of 5 N NaOH and CH2Cl2 at atmospheric pressure and 40 deg C, with (C6H13)4N+ HSO4- as the phase transfer catalyst, to give carboxylic esters as the major products. Keywords: Rhodium; Carbonylation; Zwitterionic complex; Phase transfer catalysis
- Amaratunga, Shiyamalie,Alper, Howard
-
-
- A Study of the Ferrous Ion-initiated SRN1 Reactions of Halogenoarenes with tert-Butyl Acetate and N-Acylmorpholine Enolates
-
A detailed preparative study is reported of the ferrous ion-initiated SRN1 reactions of a range of halogenoarenes with the sodium enolates of tert-butyl acetate, n-acetylmorpholine and a number of higher N-acylmorpholines.Smooth and rapid substitution occurs in many cases, and good to excellent yields were obtained of arylacetic esters or acids, arylacetamides and arylalkanamides.The broad scope and limitations of the process have been defined, and the possible role of the ferrous ion is discussed.
- Leeuwen, Milko van,McKillop, Alexander
-
p. 2433 - 2440
(2007/10/02)
-
- Photolysis of the 1-naphthylmethyl ester of substituted phenylacetic acids: intramolecular charge transfer and rates of decarboxylation of arylacyl radicals
-
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.
-
p. 992 - 999
(2007/10/02)
-