cas 14062-19-2, ETHYL P-TOLYLACETATE | Articles data

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N-Heterocyclic Carbenes as Key Intermediates in the Synthesis of Fused, Mesoionic, Tricyclic Heterocycles
Coupling between 5-bromoimidazo[1,5-a]pyridinium salts and malonate or arylacetate esters leads to a facile and straightforward access to the new mesoionic, fused, tricyclic system of imidazo[2,1,5-cd]indolizinium-3-olate. Mechanistic studies show that the reaction pathway consists of nucleophilic aromatic substitution on the cationic, bicyclic heterocycle by an enolate-type moiety and in the nucleophilic attack of a transient free N-heterocyclic carbene (NHC) species on the ester group; the relative order of these two steps depends on the nature of the starting ester. This work highlights the valuable implementation of free NHC species as key intermediates in synthetic chemistry, beyond their classical use as stabilizing ligands or organocatalysts.
Benaissa, Idir,Pallova, Lenka,Morantin, Marie-Emilie,Lafitte, Thomas,Huynh, Mathieu,Barthes, Cécile,Vendier, Laure,Lugan, No?l,Bastin, Stéphanie,César, Vincent
p. 13030 - 13036
(2019)
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Photoassisted Cross-Coupling Reaction of α-Chlorocarbonyl Compounds with Arylboronic Acids
A Suzuki-Miyaura cross-coupling reaction of α-chloroacetates or α-chloroacetamides with arylboronic acids is made possible by visible-light irradiation. This reaction provides a useful method for the synthesis of α-arylacetates and α-arylacetamides from chlorides under mild reaction conditions. An indole-3-acetic acid derivative that is the key intermediate of the plant hormone auxin can be synthesized from 1-Boc-indole in two steps by combining an iridium-catalyzed C-H borylation and a palladium-catalyzed cross-coupling reaction.
Miura, Tomoya,Murakami, Masahiro,Oku, Naoki
supporting information
p. 1616 - 1619
(2022/03/14)

Photocatalytic acyl azolium-promoted alkoxycarbonylation of trifluoroborates
Despite recent advancements in the selective generation and coupling of organic radical species, the alkoxycarbonyl radical remains underexplored relative to other carbon-containing radical species. Drawing inspiration from new strategies for generating acyl radical equivalents utilizing dual N-heterocyclic carbene catalysis and photocatalysis, we have prepared dimethylimidazolium esters that can function as an alkoxycarbonyl radical surrogate under photocatalytic conditions. We demonstrate the synthetic utility of these azolium-based partners through the preparation of esters arising from the coupling of this radical surrogate with an oxidatively generated alkyl radical.
Scheidt, Karl A.,Zhu, Joshua L.
(2021/06/28)

Coupling of Reformatsky Reagents with Aryl Chlorides Enabled by Ylide-Functionalized Phosphine Ligands
The coupling of aryl chlorides with Reformatsky reagents is a desirable strategy for the construction of α-aryl esters but has so far been substantially limited in the substrate scope due to many challenges posed by various possible side reactions. This limitation has now been overcome by the tailoring of ylide-functionalized phosphines to fit the requirements of Negishi couplings. Record-setting activities were achieved in palladium-catalyzed arylations of organozinc reagents with aryl electrophiles using a cyclohexyl-YPhos ligand bearing an ortho-tolyl-substituent in the backbone. This highly electron-rich, bulky ligand enables the use of aryl chlorides in room temperature couplings of Reformatsky reagents. The reaction scope covers diversely functionalized arylacetic and arylpropionic acid derivatives. Aryl bromides and chlorides can be converted selectively over triflate electrophiles, which permits consecutive coupling strategies.
Hu, Zhiyong,Wei, Xiao-Jing,Handelmann, Jens,Seitz, Ann-Katrin,Rodstein, Ilja,Gessner, Viktoria H.,Goo?en, Lukas J.
supporting information
p. 6778 - 6783
(2021/02/01)

Copper-Catalyzed Ullmann-Type Coupling and Decarboxylation Cascade of Arylhalides with Malonates to Access α-Aryl Esters
We have developed a high-efficiency and practical Cu-catalyzed cross-coupling to directly construct versatile α-aryl-esters by utilizing readily available aryl bromides (or chlorides) and malonates. These gram-scale approaches occur with turnovers of up to 1560 and are smoothly conducted by the usage of a low catalyst loading, a new available ligand, and a green solvent. A variety of functional groups are tolerated, and the application occurs with α-aryl-esters to access nonsteroidal anti-inflammatory drugs (NSAIDs) on the gram scale.
Chen, Fen-Er,Chen, Tao,Cheng, Fei,Huang, Yin-Qiu,Li, Jia-Wei,Xiao, Xiao,Zhou, Chen
supporting information

(2022/01/04)

Preparation method of 4-bromomethyl methyl benzoate and derivative thereof
The invention provides a preparation method of methyl 4-bromomethyl benzoate and a derivative thereof, and the method comprises an esterification reaction for converting methyl benzoic acid into methyl benzoate and a bromination reaction for converting the methyl benzoate into the methyl 4-bromomethyl benzoate and the derivative thereof, the brominating agent for the bromination reaction is dibromohydantoin, and the structural formulas of the 4-bromomethyl methyl benzoate and the derivatives thereof are shown in the specification, wherein n1 is equal to 0, 1 or 2; n2 is equal to 1 or 2; according to the preparation method disclosed by the invention, the reaction time can be greatly shortened, the reaction yield is high, and the production efficiency is improved.
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Paragraph 0044; 0046

(2021/05/05)

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)

Computer-Assisted Discovery and Structural Optimization of a Novel Retinoid X Receptor Agonist Chemotype
As universal heterodimer partners of many nuclear receptors, the retinoid X receptors (RXRs) constitute key transcription factors. They regulate cell proliferation, differentiation, inflammation, and metabolic homeostasis and have recently been proposed as potential drug targets for neurodegenerative and inflammatory diseases. Owing to the hydrophobic nature of RXR ligand binding sites, available synthetic RXR ligands are lipophilic, and their structural diversity is limited. Here, we disclose the computer-assisted discovery of a novel RXR agonist chemotype and its systematic optimization toward potent RXR modulators. We have developed a nanomolar RXR agonist with high selectivity among nuclear receptors and superior physicochemical properties compared to classical rexinoids that appears suitable for in vivo applications and as lead for future RXR-targeting medicinal chemistry.
Heitel, Pascal,Gellrich, Leonie,Kalinowsky, Lena,Heering, Jan,Kaiser, Astrid,Ohrndorf, Julia,Proschak, Ewgenij,Merk, Daniel
supporting information
p. 203 - 208
(2019/01/25)

Mechanistic studies on gold-catalyzed direct arene c-h bond functionalization by carbene insertion: The coinage-metal effect
The catalytic functionalization of the Csp2-H bond of benzene by means of the insertion of the CHCO2Et group from ethyl diazoacetate (N2= CHCO2Et) has been studied with the series of coinage-metal complexes IPrMCl (IPr = 1,3-bis- (diisopropylphenyl)imidazol-2-ylidene) and NaBArF 4 (BArF 4 = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate). For Cu and Ag, these examples constitute the first use of such metals toward this transformation, which also provides ethyl cyclohepta-2,4,6-trienecarboxylate as a byproduct from the so-called Buchner reaction. In the case of methyl-substituted benzenes, the reaction exclusively proceeds onto the aromatic ring, the Csp3-H bond remaining unreacted. A significant coinage-metal effect has been observed, since the gold catalyst favors the formation of the insertion product into the Csp2-H bond whereas copper and silver preferentially induce the formation of the cycloheptatriene derivative. Experimental studies and theoretical calculations have explained the observed selectivity in terms of the formation of a common Wheland intermediate, resembling an electrophilic aromatic substitution, from which the reaction pathway evolves into two separate routes to each product.
Fructos, Manuel R.,Besora, Maria,Braga, Ataualpa A. C,Díaz-Requejo, M. Mar,Maseras, Feliu,Perez, Pedro J.
p. 172 - 179
(2017/04/04)

Modular Synthesis of Arylacetic Acid Esters, Thioesters, and Amides from Aryl Ethers via Rh(II)-Catalyzed Diazo Arylation
One-pot formation of arylacetic acid esters, thioesters, and amides via Rh(II)-catalyzed arylation of a Meldrum's acid-derived diazo reagent with electron-rich arenes is described. The methodology was used to efficiently synthesize an anticancer compound.
Best, Daniel,Jean, Micka?l,Van De Weghe, Pierre
p. 7760 - 7770
(2016/09/12)

Iodobenzene Dichloride in the Esterification and Amidation of Carboxylic Acids: In-Situ Synthesis of Ph3PCl2
A novel, in-situ synthesis of dichlorotriphenylphosphorane (Ph3PCl2) is accomplished upon combining PPh3and the easily prepared hypervalent iodine reagent iodobenzene dichloride (PhICl2). The phosphorane is selectively generated in the presence of carboxylic acid or alcohol residues to rapidly produce acyl chlorides and alkyl chlorides in high yields. Addition of EtOH, PhOH, BnOH, Et2NH or CH2N2results in the direct synthesis of esters, amides and diazo ketones from carboxylic acids.
Carle, Myriam S.,Shimokura, Grace K.,Murphy, Graham K.
supporting information
p. 3930 - 3933
(2016/08/24)

Iron and manganese catalysts for the selective functionalization of arene C(sp2)-H bonds by carbene insertion
The first examples of the direct functionalization of non-activated aryl sp2 C-H bonds with ethyl diazoacetate (N2CHCO2Et) catalyzed by Mn- or Fe-based complexes in a completely selective manner are reported, with no formation of the frequently observed cycloheptatriene derivatives through competing Buchner reaction. The best catalysts are FeII or MnII complexes bearing the tetradentate pytacn ligand (pytacn= 1-(2-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane). When using alkylbenzenes, the alkylic C(sp3)-H bonds of the substituents remained unmodified, thus the reaction being also selective toward functionalization of sp2 C-H bonds. Exclusive catalysis: Iron- and-manganese-based catalysts selectively functionalize the C(sp2)-H bonds of benzene or alkylbenzenes through the formal insertion of the CHCO2Et group from N2CHCO2Et (see scheme). When using alkylbenzenes, the alkylic C(sp3)-H bonds of the substituents remain unmodified.
Conde, Ana,Sabenya, Gerard,Rodríguez, Mònica,Postils, Verònica,Luis, Josep M.,Díaz-Requejo, M. Mar,Costas, Miquel,Pérez, Pedro J.
supporting information
p. 6530 - 6534
(2016/06/01)

Selective synthesis of arylacetic acid esters from ethyl acetoacetate and aryl halides in the presence of copper(II) on 4 ? molecular sieves
A heterogeneous catalyst, copper(II) on 4 ? molecular sieves has successfully been used in the arylation of ethyl acetoacetate, selectively forming arylacetic esters in high yields. The air stable and easily handled catalyst can be simply filtered off during purification thus avoiding significant metal contamination of the product.
Zsolczai, Dávid,Németh, János,Hell, Zoltán
p. 6389 - 6392
(2015/11/16)

PROCESS FOR PREPARING ARYL- AND HETEROARYLACETIC ACID DERIVATIVES
The invention relates to a process for preparing aryl- and heteroarylacetic acids and derivatives thereof by reaction of aryl or heteroaryl halides with malonic diesters in the presence of a palladium catalyst, of one or more bases and optionally of a phase transfer catalyst. This process enables the preparation of a multitude of functionalized aryl- and heteroarylacetic acids and derivatives thereof, especially also the preparation of arylacetic acids with sterically demanding substituents.
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Paragraph 0075; 0076; 0086

(2014/06/23)

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.
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Paragraph 0046; 0047

(2013/11/19)

Alcohol assisted C-C bond breaking: Copper-catalyzed deacetylative α-arylation of β-keto esters and amides
A method of alcohol-assisted copper-catalyzed highly selective deacetylative α-arylation of β-keto esters and amides has been demonstrated, which illustrated an efficient example of achieving α-aryl esters and amides. From the synthetic point of view, this arylation protocol is general and practical, representing a simple way to produce α-arylated carbonyl compounds from basic starting materials at low cost.
Ke, Jie,He, Chuan,Liu, Huiying,Xu, Huan,Lei, Aiwen
supporting information
p. 6767 - 6769
(2013/07/26)

Synthesis of arylacetates from benzylic alcohols and oxalate esters through decarboxylative coupling
Follow that dream: By combining a reversible transesterification between benzylic alcohols and dialkyl oxalates with catalytic decarboxylation of the resulting esters, a regiospecific C-C-bond-forming reaction to give α-arylacetates was achieved. In the overall process, CO2 and a volatile alcohol are the only byproducts. Various α-arylacetates were thus synthesized in high yields from easily accessible starting materials in the presence of catalytic amounts of Pd(OAc)2, dppp, and DABCO (see scheme). Copyright
Gruenberg, Matthias F.,Goossen, Lukas J.
supporting information
p. 7334 - 7337
(2013/06/27)

Palladium-catalyzed oxidative carbonylation of benzylic C-H bonds via nondirected C(sp3)-H activation
A new strategy for generating benzylpalladium reactive species from toluenes via nondirected C(sp3)-H activation has been developed. This led to construction of an efficient Pd-catalyzed reaction protocol for the oxidative carboxylation of benzylic C-H bonds to form substituted 2-phenylacetic acid esters and derivatives from inexpensive, commercially available starting materials.
Xie, Pan,Xie, Yinjun,Qian, Bo,Zhou, Han,Xia, Chungu,Huang, Hanmin
supporting information; experimental part
p. 9902 - 9905
(2012/08/08)

Pd-catalyzed decarboxylative cross-couplings of potassium malonate monoesters with aryl halides
An efficient catalytic protocol for Pd-catalyzed decarboxylative cross-coupling of potassium malonate monoesters and derivatives with aryl bromides and chlorides are described. Because of its broad applicability, this new catalytic system provides an alternative method for the preparation of diverse aryl acetic acids and derivatives.
Feng, Yi-Si,Wu, Wei,Xu, Zhong-Qiu,Li, Yan,Li, Ming,Xu, Hua-Jian
experimental part
p. 2113 - 2120
(2012/03/26)

Palladium/copper-catalyzed Di-α-arylation of acetic acid esters
A bimetallic palladium/copper catalyst system was found to effectively promote the diarylation of alkyl acetates with aryl halides under unprecedentedly mild conditions. The phenanthroline-copper-phosphine catalyst stabilizes the enolate intermediate to the extent that the deprotonation of esters can be achieved even with the mild base potassium phosphate. The palladium tri-tert-butylphosphine co-catalyst mediates the coupling of the resulting copper enolate with a wide variety of aryl halides with selective formation of the corresponding diarylacetic acid esters. Copyright
Song, Bingrui,Himmler, Thomas,Goossen, Lukas J.
scheme or table
p. 1688 - 1694
(2011/09/14)

Practical synthesis of 2-arylacetic acid esters via palladium-catalyzed dealkoxycarbonylative coupling of malonates with aryl halides
A new palladium-based system was developed that catalyzes the coupling of aryl halides with diethyl malonates in the presence of mild bases. In the course of the reaction, the intermediately formed diethyl arylmalonate is directly converted into the arylacetic acid ester via liberation of carbon dioxide and an alkanol. This cross-coupling/dealkoxycarbonylation process provides an efficient and high-yielding synthetic entry to diversely functionalized arylacetic acid esters. Two complementary protocols were developed, one of which is optimal for electron-rich, the other for electron-poor aryl halides. Both make use of low loadings of palladium(0) bis(dibenzylideneacetone) (0.5 mol%)/tri-tert-butylphosphonium tetrafluoroborate (1.1 mol%) as the catalyst and diethyl malonate as the reaction solvent. The new procedures are particularly effective for sterically hindered substrates. Copyright
Song, Bingrui,Rudolphi, Felix,Himmler, Thomas,Goossen, Lukas J.
supporting information; experimental part
p. 1565 - 1574
(2011/08/03)

Exclusive aromatic vs aliphatic C-H bond functionalization by carbene insertion with gold-based catalysts
The direct functionalization of aromatic C-H bonds by carbene insertion from diazo compounds catalyzed by gold complexes with N-heterocyclic ligands is described. The reaction is completely selective toward the C sp2-H bonds, other C sp3-H bonds remaining unreacted. A study with several NHC ligands in Au(I) and Au(III) complexes has been performed. The potential application of this strategy to give profen derivatives has also been explored.
Rivilla, Ivan,Gomez-Emeterio, B. Pilar,Fructos, Manuel R.,Diaz-Requejo, M. Mar,Perez, Pedro J.
experimental part
p. 2855 - 2860
(2011/07/08)

Palladium-catalyzed cross-coupling of sterically demanding boronic acids with α-bromocarbonyl compounds
A catalyst system generated in situ from Pd(dba)2 and tri(o-tolyl)phosphine mediates the coupling of arylboronic acids with alkyl α-bromoacetates under formation of arylacetic acid esters at unprecedented low loadings. The new protocol, which involves potassium fluoride as the base and catalytic amounts of benzyltriethylammonium bromideas a phase transfer catalyst, is uniquely effective for the synthesis of sterically demanding arylacetic acid derivatives. (Figure presented)
Zimmermann, Bettina,Dzik, Wojciech I.,Himmler, Thomas,Goossen, Lukas J.
experimental part
p. 8107 - 8112
(2011/11/07)

Water works: An efficient palladium-catalyzed cross-coupling reaction between boronic acids and bromoacetate with aminophosphine ligand
Water greatly restrained the formation of self-coupling of boronic acids in a palladium-catalyzed cross-coupling reaction between boronic acids and ethyl bromoacetate with an aminophosphine ligand; good to excellent yields of cross-coupling product were obtained.
Peng, Zhi-Yong,Wang, Jian-Ping,Cheng, Jiang,Xie, Xiao-Min,Zhang, Zhaoguo
experimental part
p. 8238 - 8241
(2010/10/21)

PROCESS FOR PRODUCING ESTER COMPOUND
PROBLEM To provide an environmentally-friendly method for producing industrially an ester compound. SOLUTION The present invention is a method for producing an ester compound which comprises subjecting a carboxylic acid and an alcohol to dehydration-condensation reaction using an involatile acid catalyst and then removing the residual acid catalyst by bringing a weak basic substance into contact with the residual acid catalyst.
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Page/Page column 16

(2010/12/31)

Thiadiazole-based Thioglycosides as Sodium-glucose Co-transporter 2 (SGLT2) Inhibitors
A series of thiadiazole-based thioglycosides were synthesized as SGLT2 inhibitors from D-glucose, D-galactose and a variety of phenylacetic acids via a convenient protocol in 8 steps and evaluated in vivo with an oral glucose tolerance test (OGTT), and 5-benzyl-1,3,4-thiadiazol-2-yl 1-thio-β-D-glucopyranoside (1a) was the most efficacious to suppress the blood glucose excursion during OGTT.
Gao, Yunlong,Zhao, Guilong,Liu, Wei,Wang, Yuli,Xu, Weiren,Wang, Jianwu
scheme or table
p. 605 - 612
(2010/10/19)

4-Amino-5-aryl-6-arylethynylpyrimidines: Structure-activity relationships of non-nucleoside adenosine kinase inhibitors
A series of non-nucleoside adenosine kinase (AK) inhibitors is reported. These inhibitors originated from the modification of 5-(3-bromophenyl)-7-(6-morpholin-4-ylpyridin-3-yl)pyrido[2,3-d]pyrimidin-4-ylamine (ABT-702). The identification of a linker that would approximate the spatial arrangement found between the pyrimidine ring and the aryl group at C(7) in ABT-702 was a key element in this modification. A search of potential linkers led to the discovery of an acetylene moiety as a suitable scaffold. It was hypothesized that the aryl acetylenes, ABT-702, and adenosine bound to the active site of AK (closed form) in a similar manner with respect to the orientation of the heterocyclic base. Although potent acetylene analogs were discovered based on this assumption, an X-ray crystal structure of 5-(4-dimethylaminophenyl)-6-(6-morpholin-4-ylpyridin-3-ylethynyl)pyrimidin-4-ylamine (16a) revealed a binding orientation contrary to adenosine. In addition, this compound bound tightly to a unique open conformation of AK. The structure-activity relationships and unique ligand orientation and protein conformation are discussed.
Matulenko, Mark A.,Paight, Ernest S.,Frey, Robin R.,Gomtsyan, Arthur,DiDomenico Jr., Stanley,Jiang, Meiqun,Lee, Chih-Hung,Stewart, Andrew O.,Yu, Haixia,Kohlhaas, Kathy L.,Alexander, Karen M.,McGaraughty, Steve,Mikusa, Joseph,Marsh, Kennan C.,Muchmore, Steven W.,Jakob, Clarissa L.,Kowaluk, Elizabeth A.,Jarvis, Michael F.,Bhagwat, Shripad S.
p. 1586 - 1605
(2008/02/01)

A gold catalyst for carbene-transfer reactions from ethyl diazoacetate
(Chemical Equation Presented) Approaching El Dorado: A gold catalyst has been discovered that transfers a carbene unit from ethyl diazoacetate to aromatic substrates (see scheme) as well as olefins, amines, and alcohols. The insertion of carbene units into the C-H bonds of the aromatic ring of benzene, toluene, and styrene is a novel reaction. R = H, CH3, CH=CH 2; IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene.
Fructos, Manuel R.,Belderrain, Tomas R.,De Fremont, Pierre,Scott, Natalie M.,Nolan, Steven P.,Diaz-Requejo, M Mar,Perez, Pedro J.
p. 5284 - 5288
(2007/10/03)

1,2-disubstituted-6-oxo-3-phenyl-piperidine-3-carboxamides and combinatorial libraries thereof
The invention relates to combinatorial libraries containing two or more novel piperidine-3-carboxamide derivative compounds, methods of preparing the piperidine-3-carboxamide derivative compounds and piperidine-3-carboxamide derivative compounds bound to a resin
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(2008/06/13)

Remarkable co-catalysis by copper(I) oxide in the palladium catalyzed cross-coupling of arylboronic acids with ethyl bromoacetate
Copper(I) oxide can effectively co-catalyze the Suzuki type cross-coupling reactions of arylboronic acids with ethyl bromoacetate. As an alternative protocol for introducing the methylenecarboxy group into functionalized molecules, this reaction occurs in
Liu, Xing-Xin,Deng, Min-Zhi
p. 622 - 623
(2007/10/03)

One-carbon homologation of carboxylic acids via BtCH2TMS: A safe alternative to the Arndt-Eistert reaction
Carboxylic acids are converted into the corresponding homologated acids or esters, using easily available 1-(trimethylsilylmethyl)benzotriazole (1) as a one-carbon synthon. The effectiveness of the reaction has been investigated on six aryl and seven alkyl carboxylic acids.
Katritzky,Zhang,Haleem,Hussein,Fang,Steel
p. 5606 - 5612
(2007/10/03)

Pd-catalyzed synthesis of arylacetic acid derivatives from boronic acids
A palladium(0)-catalyzed cross-coupling reaction between arylboronic acids or esters and α-bromoacetic acid derivatives is described which allows the synthesis of various functionalized arylacetic acid derivatives under mild conditions.
Goossen
p. 669 - 670
(2007/10/03)

BtCH2TMS-assisted Homologation of Carboxylic Acids: A Safe Alternative to the Arndt-Eistert Reaction
formula presented One-carbon homologation of carboxylic acids is achieved by (i) treatment of an acyl chloride with 1-[(trimethylsilyl)methyl]-1H-1,2,3,-benzotriazole (BtCH2TMS) (1) to afford N-(acylmethyl)benzotriazoles 3a-f, followed by (ii) conversion of 3a-f with triflic anhydride into RC(OTf)=CHBt 4a-f, and (iii) the subsequent reaction of 4a-c with NaOCH3 followed by 1N HCl to afford esters RCH2CO2R′ 7a-c in overall yields of 50-70%. For the aliphatic compounds 5d-f, treatment of 5d-f with p-toluenesulfonic acid followed by TBAF/THF afforded acids RCH2COOH 7d-f.
Katritzky, Alan R.,Zhang, Suoming,Fang, Yunfeng
p. 3789 - 3791
(2007/10/03)

Pyrimido[1,2-a]indoles
The pyrimido[1,2-a]indoles according to the invention are prepared by reacting appropriately substituted phenylacetic acid derivatives with phenylglycinols. The pyrimido[1,2-a]indoles can be used as active compounds in medicaments, in particular in medicaments with antiatherosclerotic activity.
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(2008/06/13)

Synthesis, biological activity, and SARs of pyrrolobenzoxazepine derivatives, a new class of specific 'peripheral-type' benzodiazepine receptor ligands
The 'peripheral-type' benzodiazepine receptor (PBR) has been reported to play a role in many biological processes. We have synthesized and tested a novel series of PBR ligands based on a pyrrolobenzoxazepine skeleton, in order to provide new receptor ligands. Several of these new compounds proved to be high affinity and selective ligands for PBR, and benzoxazepines 17f and 17j were found to be the most potent ligands for this receptor to have been identified to date. The SAR and the molecular modeling studies detailed herein delineated a number of structural features required for improving affinity. Some of the ligands were employed as 'molecular yardsticks' to probe the spatial dimensions of the lipophilic pockets L1 and L3 in the PBR cleft and to determine the effect of occupation of L1 and L3 with respect to affinity, while other C-7 modified analogues provided information specifically on the hydrogen bonding with a putative receptor site H1. The new pyrrolobenzoxazepines were tested in rat cortex, a tissue expressing high density of mitochondrial PBR, and exhibited IC50 and K(i) values in the low nanomolar or subnanomolar range, as measured by the displacement of [3H]PK 11195 binding. A subset of the highest affinity ligands was also found to have high affinities for [3H]PK 11195 and [3H]Ro 5-4864 binding in rat adrenal mitochondria. All the ligands in this subset are stimulators of steroidogenesis having similar potency and extent of stimulation as PK 11195 and Ro 5-4864 of steroidogenesis in the mouse Y-1 adrenocortical cell line.
Campiani, Giuseppe,Nacci, Vito,Fiorini, Isabella,De Filippis, Maria P.,Garofalo, Antonio,Ciani, Silvia M.,Greco, Giovanni,Novellino, Ettore,Williams, D. Clive,Zisterer, Daniela M.,Woods, Margaret J.,Mihai, Camelia,Manzoni, Cristina,Mennini, Tiziana
p. 3435 - 3450
(2007/10/03)

Synthesis of ethoxyethynylarenes by the palladium-catalyzed reaction of aryl iodides with ethoxy(trialkylstannyl)acetylenes
Palladium-catalyzed reaction of aryl and heteroaryl iodides with ethoxy(trialkylstannyl)acetylenes gave the ethoxyethynylarenes and -heteroarenes, which were easily transformed by hydration reaction into ethyl areneacetates and heteroareneacetates.
Sakamoto,Yasuhara,Kondo,Yamanaka
p. 2032 - 2035
(2007/10/02)

IODIDE ION PROMOTION BENZYL CHLORIDE-BORATE ESTER CARBONYLANION REACTIONS
Esters are isolated in fine yields from the rhodium(I) catalyzed reaction of benzyl chlorides with borate esters and carbon monoxide, in the presence of potassium iodide.
Alper, Howard,Hamel, Nathalie,Smith, David J. H.,Woell, James B.
p. 2273 - 2274
(2007/10/02)

Palladium-catalyzed Displacement of Aryl Halide by Tin Analogue of Reformatsky Reagent
Reaction of ethyl α-(tributylstannyl)acetate with aryl bromides in the presence of zinc bromide or chloride and a catalytic amount of dichlorobis(tri-o-tolylphosphine)palladium was found to give ethyl arylacetates in good yields except with the aryl bromide having p-acetyl or p-nitro group.
Kosugi, Masanori,Negishi, Yoshikazu,Kameyama, Masayuki,Migita, Toshihiko
p. 3383 - 3384
(2007/10/02)

Desulfurization and Carbonylation of Mercaptans
The first examples of the carbonylation of mercaptans are described: cobalt carbonyl catalyzes the desulfurization and carbonylation of mercaptans to carboxylic esters by means of carbon monoxide in aqueous alcohol.
Shim, Sang Chul,Antebi, Shlomo,Alper, Howard
p. 147 - 149
(2007/10/02)

Metall-katalysierte Carbonylierungen von Benzyl- und Arylbromiden in Gegenwart von Aluminiumalkoxiden, eine einfache Estersynthese
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Alper, Howard,Antebi, Shlomo,Woell, James B.
p. 710 - 711
(2007/10/02)

SYNTHESIS OF ESTERS BY RHODIUM(I) CATALYZED BORATE ESTER-BENZYLIC BROMIDE CARBONYLATION REACTIONS
Benzylic halides react with trialkylborates and carbon monoxide, in the presence of 1,5-hexadienerhodium chloride dimer, to give esters in excellent yields.The reaction is applicable to the synthesis of primary, secondary and even tertiary esters.
Woell, James B.,Alper, Howard
p. 3791 - 3794
(2007/10/02)