- 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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- 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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- Quinolones as gonadotropin releasing hormone (GnRH) antagonists: Simultaneous optimization of the C(3)-aryl and C(6)-substituents
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A series of 3-arylquinolones was prepared and evaluated for their ability to act as gonadotropin releasing hormone (GnRH) antagonists. A variety of substitution patterns of the 3-aryl substituent are described. The 3,4,5-trimethylphenyl substituent (23h) was found to be optimal. (C) 2000 Elsevier Science Ltd. All rights reserved.
- Young, Jonathan R.,Huang, Song X.,Chen, Irene,Walsh, Thomas F.,DeVita, Robert J.,Wyvratt Jr., Matthew J.,Goulet, Mark T.,Ren, Ning,Lo, Jane,Yang, Yi Tien,Yudkovitz, Joel B.,Cheng, Kang,Smith, Roy G.
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p. 1723 - 1727
(2007/10/03)
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- Synthesis of phenylacetic acids under rhodium-catalyzed carbonylation conditions
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Benzyl halides are efficiently carbonylated to phenylacetic acids in the presence of a catalytic amount of the dimer of chloro(1,5-cyclooctadiene)rhodium(I) in formic acid. Under these reaction conditions, sensitive functionalities such as esters and nitriles are tolerated and the phenylacetic acids are obtained in good to high yields. (C) 2000 Elsevier Science Ltd.
- Giroux,Nadeau,Han
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p. 7601 - 7604
(2007/10/03)
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- Direct Carbonylation of Benzyl Alcohol and Its Analogs Catalyzed by Palladium and HI in Aqueous Systems and Mechanistic Studies
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Carbonylation of benzyl alcohol, benzyl formate, dibenzyl ether, and benzyl phenylacetate catalyzed by palladium complexes and promoted by hydrogen iodide gives phenylacetic acid in moderate to excellent yields in aqueous systems. Application of the carbonylation process to other arylmethanol analogs provides convenient means to prepare 2-naphthaleneacetic acid, 3-isochromanone, 1,4-benzenediacetic acid, and o-hydroxybenzeneacetic acid. A mechanism for the catalytic reaction is proposed, which involves (1) formation of benzyl iodide by the reaction of benzyl alcohol with HI in situ, (2) oxidative addition of benzyl iodide to palladium(0) to form a benzylpalladium iodide species. (3) CO insertion into the Pd-benzyl bond to form a (phenylacetyl)palladium iodide species. (4) reductive elimination of phenylacetyl iodide, and (5) its hydrolysis into phenylacetic acid. Evidence supporting the mechanism was obtained by examining the properties of benzyl- and (phenylacetyl)palladium iodide and chloride complexes. Formation of benzyl(carbonyl)palladium species and migratory insertion of the benzyl group to CO was confirmed by means of NMR at low temperature under high pressure.
- Lin, Yong-Shou,Yamamoto, Akio
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p. 723 - 734
(2007/10/03)
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- Palladium-catalyzed carbonylation of benzyl alcohol and its analogs promoted by HI in aqueous systems
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Carbonylation of benzyl alcohol catalyzed by a palladium(0) complex and promoted by hydrogen iodide gives phenylacetic acid in excellent yields in aqueous systems. The catalysis is proposed to proceed through a benzylpalladium species formed by the oxidative addition of benzyl iodide, produced in situ by the interaction of benzyl alcohol with HI, to a Pd(0) species. Application of the carbonylation process to other arylmethanol analogs provided convenient means to prepare 3-isochromanone, 1,4-benzenediacetic acid, 2-hydroxybenzeneacetic acid and 2-naphthaleneacetic acid.
- Lin, Yong-Shou,Yamamoto, Akio
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p. 3747 - 3750
(2007/10/03)
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- N-acyl sulfamic acid esters (or thioesters), N-acyl sulfonamides, and N-sulfonyl carbamic acid esters (or thioesters) as hypercholesterolemic agents
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The present invention is directed to compounds useful for the regulation of cholesterol of Formula I, methods for using them and pharmaceutical compositions thereof, STR1 wherein X and Y are oxygen, sulfur, or (CR'R")n wherein n is 1 to 4; R is hydrogen, alkyl, or benzyl; R1 and R2 are phenyl, substituted phenyl, naphthyl, substituted naphthyl, an aralkyl group, an alkyl chain, adamantyl, or a cycloalkyl group.
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- A Study of the Ferrous Ion-initiated SRN1 Reactions of Halogenoarenes with tert-Butyl Acetate and N-Acylmorpholine Enolates
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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
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p. 2433 - 2440
(2007/10/02)
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- GAS-PHASE REPLACEMENT ?0 SUBSTITUENT CONSTANTS OF HETEROARYL GROUPS
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Hammett replacement ?0 substituent constants of pyridyl, thienyl, and furyl groups are reported for the first time from gas-phase eliminations of their t-butyl and isopropyl heteroarylcarboxylate esters.
- Al-Awadi, Nouria A.,Al-Bashir, Rasha F.,ElDusouqui, Osman M. E.
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p. 1699 - 1702
(2007/10/02)
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- Novel thiophene-acetic acids
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Novel thiophene-acetic acid derivatives of the formulae STR1 wherein R is selected from the group consisting of hydrogen and alkyl of 1 to 4 carbon atoms, R1 is selected from the group consisting of lower alkyl of 1 to 4 carbon atoms and hydrogen and R2 is selected from the group consisting of hydrogen, lower alkyl of 1 to 7 carbon atoms and optionally substituted with at least one hydroxy group or an oxygen atoms-containing heterocycle,di-lower alkylamino-lower alkyl, N-heterocyclic alkyl, alkali metals, alkaline earth metals, aluminum and --H,NH (lower alkyl)2 and Ar is selected from the group consisting of phenyl, optionally substituted with at least one member of the group consisting of halogen, trihalogenomethyl, lower alkyl, lower alkoxy and carboxyl, cyclohexyl, thienyl, furyl, tetrahydrofuryl and pyridyl, and in formula II, ArCO is attached to one of the positions α to the sulfur atom, which compounds have analgesic and anti-inflammatory activity and their preparations.
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- Methods and intermediates for preparing cis-4-oxoazetidine intermediates
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The stereospecific cycloaddition of nitrogen containing acetic acid halides or anhydrides with Schiff bases having a carbalkoxy group substituted on the methine carbon atom offers new intermediates and methods for preparing synthetic cephalosporin congeners having antibacterial activity.
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- Cis-4-oxoazetidine intermediates and methods of preparing them
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The stereospecific cycloaddition of nitrogen containing acetic acid halides or anhydrides with Schiff bases having a carbalkoxy group substituted on the methine carbon atom offers new intermediates and methods for preparing synthetic cephalosporin congeners having antibacterial activity.
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- 8-Oxo-4-thia-1-azabicyclo (4.2.0)-oct-2-ene derivatives
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Novel bicyclic β-lactams and intermediates useful in their preparation are disclosed. In particular, 7β-acyl-amino- and 7β-amino-8-oxo-4-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acids are prepared. The acylated compounds are antibacterial agents.
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