- Cyclohexyl-Fused, Spirobiindane-Derived, Phosphine-Catalyzed Synthesis of Tricyclic ?3-Lactams and Kinetic Resolution of ?3-Substituted Allenoates
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A C2-symmetric chiral phosphine catalyst, NUSIOC-Phos, which can be easily derived from cyclohexyl-fused spirobiindane, was introduced. A highly enantioselective domino process involving pyrrolidine-2,3-diones and γ-substituted allenoates catalyzed by NUSIOC-Phos has been disclosed. Diastereospecific tricyclic γ-lactams containing five contiguous stereogenic centers were obtained in high yields and with nearly perfect enantioselectivities. A kinetic resolution process of racemic γ-substituted allenoates was developed for the generation of optically enriched chiral allenoates.
- Wu, Mingyue,Han, Zhaobin,Li, Kaizhi,Wu, Ji'En,Ding, Kuiling,Lu, Yixin
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supporting information
p. 16362 - 16373
(2019/10/16)
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- Regioselectivity inversion tuned by iron(iii) salts in palladium-catalyzed carbonylations
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Impactful regioselectivity control is crucial for cost-effective chemical synthesis. By using cheap and abundant iron(iii) salts, the hydroxycarbonylations of both aromatic and aliphatic alkenes were significantly enhanced in both reactivity and selectivity (iso/n or n/iso up to >99:1). Moreover, Pd-catalyzed carbonylation selectivity can be switched from branched to linear by using different Fe(iii) salts. In addition, similar results were obtained for the carbonylation of secondary alcohols.
- Huang, Zijun,Cheng, Yazhe,Chen, Xipeng,Wang, Hui-Fang,Du, Chen-Xia,Li, Yuehui
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supporting information
p. 3967 - 3970
(2018/04/23)
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- Pd-Catalyzed β-C(sp3)?H Arylation of Propionic Acid and Related Aliphatic Acids
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A generally applicable Pd-catalyzed protocol for the β-C(sp3)?H arylation of propionic acid and related α-branched aliphatic acids is reported. Enabled by the use of N-acetyl-β-alanine as ligand our protocol delivers a broad range of arylation products. Notably, the highly challenging substrate, propionic acid, which lacks any acceleration through the Thorpe–Ingold effect, can be employed as substrate with synthetically useful yields. Furthermore, the scalability and synthetic applicability of the protocol are demonstrated.
- Ghosh, Kiron K.,van Gemmeren, Manuel
-
supporting information
p. 17697 - 17700
(2017/12/07)
-
- Hydrocarboxylation of olefins by supported aqueous-phase catalysis
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Pd-TPPTS complexes supported on acidic macro-porous resins (Pd-TPPTS/resin) have been employed for the hydrocarboxylation of 1-hexene and styrene derivatives by supported aqueous phase catalysis (SAPC). Acidic macroporous resins acted as substitutes for both heterogeneous acids and supports of Pd-TPPTS complexes afforded many advantages, such as easy separation from organic products and good reusability. The prepared Pd-TPPTS/resin catalysts were characterized by FT-IR, TG, SEM and N2 physisorption, which demonstrated that the Pd-TPPTS complexes were loaded on the resin. Compared with homogeneous analogue, the present SAP catalyst offered higher total acid yield and selectivity towards linear acid in the hydrocarboxylation of 1-hexene. Moreover, it was found that water had a significant influence on the catalytic activity and selectivity toward linear acid over the SAP catalyst. Optimum water/resin ratio at about 66.7% in the SAP catalyst afforded maximum activity under the given reaction temperature. The present SAP catalyst was highly Pd-leaching resistant and can be reused at least four times without obvious loss in activity.
- He, Zhenhong,Hou, Zhenshan,Zhang, Yagang,Wang, Tianfu,Dilixiati, Yierxiati,Eli, Wumanjiang
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p. 147 - 154
(2015/03/30)
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- SUBSTITUTED BENZAMIDES AND THEIR USES
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Provided herein are Substituted Benzamides, compositions, and method of their manufacture and use.
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- A robust and simple protocol for the synthesis of arylfluorophosphonates
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Fluorophosphonates represent powerful probes for the identification and analysis of active serine hydrolases in activity based protein profiling. Although alkylphosphonofluoridates are widely used for such purposes, little is known about the synthesis and purification of arylphosphonofluoridates, which may be useful tools for screening enzyme activities toward aromatic esters. Our optimized route makes this subclass of transition state inhibitors broadly accessible for a diverse series of phosphonic acid derivatives using a combination of selective monoesterification with EDC·HCl and subsequent mild fluorination with DAST. All compounds were isolated as pure materials using a simple acid-base extraction protocol in 76-93% yields over two steps. These probes can be stored under an inert atmosphere at -24 °C for several months without significant degradation.
- Leypold, Mario,Wallace, Paal W.,Kljajic, Marko,Schittmayer, Matthias,Pletz, Jakob,Illaszewicz-Trattner, Carina,Guebitz, Georg M.,Birner-Gruenberger, Ruth,Breinbauer, Rolf
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supporting information
p. 5619 - 5622
(2015/09/21)
-
- SUBSTITUTED BENZAMIDES AND THEIR USES
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Provided herein are Substituted Benzamides, compositions, and method of their manufacture and use.
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- A simple and straightforward approach toward selective C=C bond reduction by hydrazine
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A simple and straightforward method for reducing the C=C double bond with hydrazine is described. A number of representative C=C bonds in various steric and electronic environments were examined. Substituted alkenes can be selectively reduced in EtOH in the presence of hydrazine to give the corresponding products in up to 100% yields.
- Chen, Hao,Wang, Jianmin,Hong, Xuechuan,Zhou, Hai-Bing,Dong, Chune
-
supporting information
p. 758 - 761
(2012/11/07)
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- Rhodium(I)-catalyzed 1,4-addition of arylboronic acids to acrylic acid in water: One-step preparation of 3-arylpropionic acids
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A practical method for the one-step preparation of 3-arylpropionic acids through rhodium-catalyzed 1,4-addition of arylboronic acids to acrylic acid is reported. The method is applicable to a broad scope of aryl boronic acids and displays a wide functional group tolerance operating in water as the optimal reaction medium. Georg Thieme Verlag Stuttgart · New York.
- Vautravers, Nicolas R.,Breit, Bernhard
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supporting information; experimental part
p. 2517 - 2520
(2011/11/12)
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- Auxiliary-assisted palladium-catalyzed arylation and alkylation of sp 2 and sp3 carbon-hydrogen bonds
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We have developed a method for auxiliary-directed, palladium-catalyzed β-arylation and alkylation of sp3 and sp2 C-H bonds in carboxylic acid derivatives. The method employs a carboxylic acid 2-methylthioaniline- or 8-aminoquinoline amide substrate, aryl or alkyl iodide coupling partner, palladium acetate catalyst, and an inorganic base. By employing 2-methylthioaniline auxiliary, selective monoarylation of primary sp3 C-H bonds can be achieved. If arylation of secondary sp 3 C-H bonds is desired, 8-aminoquinoline auxiliary may be used. For alkylation of sp3 and sp2 C-H bonds, 8-aminoquinoline auxiliary affords the best results. Some functional group tolerance is observed and amino- and hydroxy-acid derivatives can be functionalized. Preliminary mechanistic studies have been performed. A palladacycle intermediate has been isolated, characterized by X-ray crystallography, and its reactions have been studied.
- Shabashov, Dmitry,Daugulis, Olafs
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supporting information; experimental part
p. 3965 - 3972
(2010/05/15)
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- INHIBITORS OF BETA-SECRETASE
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The present invention is directed to a compound represented by the following structural formula or a pharmaceutically acceptable salt thereof. Pharmaceutical compositions and method of use of the compounds are also described.
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Page/Page column 77
(2010/10/03)
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- Design, synthesis, and biological evaluation of novel diarylalkyl amides as TRPV1 antagonists
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We have developed a new class of diarylalkyl amides as novel TRPV1 antagonists. They exhibited potent 45Ca2+ uptake inhibitions in rat DRG neuron. In particular, the amide 59 was identified as a potent antagonist with IC50 of 57 nM. The synthesis and structure-activity relationship of the diarylalkyl amides are also described.
- Li, Fu-Nan,Kim, Nam-Jung,Paek, Seung-Mann,Kwon, Do-Yeon,Min, Kyung Hoon,Jeong, Yeon-Su,Kim, Sun-Young,Park, Young-Ho,Kim, Hee-Doo,Park, Hyeung-Geun,Suh, Young-Ger
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experimental part
p. 3557 - 3567
(2009/09/27)
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- Reactive trityl derivatives: Stabilised carbocation mass-tags for life sciences applications
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The rational design of novel triarylmethyl (trityl)-based mass tags (MT) for mass-spectrometric (MS) applications is described. We propose a "pKR+ rule" to correlate the stability of trityl carbocations with their MS performance: trityls with higher pKR+ values ionise and desorb better. Trityl blocks were synthesised that have high pKR+ values and are stable in conditions of MS analysis; these MTs can be ionised by matrix as well as irradiation with a 337 nm nitrogen laser. 13C-Labelled tags were prepared for MS quantitation applications. Moreover, the tags were equipped with a variety of functional groups allowing conjugation with different functionalities within (bio)molecules to enhance the MS characteristics of the latter. The MS behaviour of model polycationic trityl compounds with and without the matrix was studied to reveal that poly-trityl clusters are always singly charged under the (MA)LDI-TOF conditions. Several peptide-trityl conjugates were prepared and comparisons revealed a beneficial effect of trityl tags on the conjugate detection in MS. Trityl compounds containing para-methoxy- and dimethylamine groups, as well as a xanthene fragment, showed considerable enhancement in MS detection of model peptides; thus they are promising tools for proteomic applications. Dimethoxytrityl derivatives allow one to distinguish between Arg- and Lys-containing peptides. Maleimido trityl derivatives are suitable for the efficient derivatisation of thiol-containing peptides in pyridine.
- Ustinov, Alexey V.,Shmanai, Vadim V.,Patel, Kaajal,Stepanova, Irina A.,Prokhorenko, Igor A.,Astakhova, Irina V.,Malakhov, Andrei D.,Skorobogatyi, Mikhail V.,Bernad, Pablo L.,Khan, Safraz,Shahgholi, Mona,Southern, Edwin M.,Korshun, Vladimir A.,Shchepinov, Mikhail S.
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supporting information; experimental part
p. 4593 - 4608
(2009/03/12)
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- Efficient synthesis of halo indanones via chlorosulfonic acid mediated Friedel-Crafts cyclization of aryl propionic acids and their use in alkylation reactions
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Several halo indanones were synthesized from benzyl Meldrum's acid derivatives in two steps. Although several Lewis acids are effective for the Friedel-Crafts ring-closing reaction on more electron-rich arenes, in the case of the electron-deficient arenes this chemistry is not efficient. Here it is reported that chlorosulfonic acid (used as solvent) is an efficient reagent for cyclization of electron-withdrawing arenes. These molecules are potentially useful for subsequent alkylation reactions. The selective alkylation of 5,7-dibromo indanone is demonstrated using Pd-catalyzed Grignard coupling to provide monoalkylated indanone in good yield.
- Sharma, Anil K.,Subramani, Amutha V.,Gorman, Christopher B.
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p. 389 - 395
(2007/10/03)
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- TRICYCLIC PYRAZOLE KINASE INHIBITORS
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Compounds of the present invention are useful for inhibiting protein tyrosine kinases. Also disclosed are methods of making the compounds, compositions containing the compounds, and methods of treatment using the compounds.
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Page/Page column 54-55
(2008/06/13)
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- The discovery and synthesis of novel adenosine receptor (A2A) antagonists
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In high throughput screening of our file compounds, a novel structure 1 was identified as a potent A2A receptor antagonist with no selectivity over the A1 adenosine receptor. The structure-activity relationship investigation using 1 as a template lead to identification of a novel class of compounds as potent and selective antagonists of A2A adenosine receptor. Compound 26 was identified to be the most potent A2A receptor antagonist (Ki = 0.8 nM) with 100-fold selectivity over the A1 adenosine receptor.
- Matasi, Julius J.,Caldwell, John P.,Hao, Jinsong,Neustadt, Bernard,Arik, Leyla,Foster, Carolyn J.,Lachowicz, Jean,Tulshian, Deen B.
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p. 1333 - 1336
(2007/10/03)
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- Derivatised molecules for mass spectrometry
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Compounds of formula (IIa): are provided where:X is a group capable of being cleaved from the α-carbon atom to form an ion of formula (I')C is a carbon atom bearing a single positive charge or a single negative charge; The invention further provides compounds of formula (IIb): where:X is a counter-ion to C. The compounds of formula (IIa) and (IIb) may form ions of formula (I') by either cleaving the C-X bond between X and the α-carbon atoms in the case of the compounds of formula (IIa) or dissociating X in the case of compounds of formula (IIb).
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- Inhibitors of histone deacetylase
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The invention relates to the inhibition of histone deacetylase. The invention provides compounds and methods for inhibiting histone deacetylase enzymatic activity. The invention also provides compositions and methods for treating cell proliferative diseases and conditions.
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- Indanylidenes. 1. Design and synthesis of (E)-2-(4,6-difluoro-1-indanylidene)acetamide, a potent, centrally acting muscle relaxant with antiinflammatory and analgesic activity
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The design of rigid cyclic analogues derived from cinnamamide 1, (E)-N-cyclopropyl-3-(3-fluorophenyl)prop-2-enamide, and β-methylcinnamamide 2, (E)-N-cyclopropyl-3-(3-fluorophenyl)but-2-enamide, has led to the discovery of the potent, centrally acting muscle relaxant (E)-2-(4,6-difluoro-1-indanylidene)acetamide, 17. Compound 17 also possesses potent antiinflammatory and analgesic activity. This paper describes the synthesis and the muscle relaxant, antiinflammatory, and analgesic structure-activity relationships of 17 and 67 of its analogues. Compound 17 has been taken into phase I clinical trials.
- Musso, David L.,Cochran, Felicia R.,Kelley, James L.,McLean, Ed W.,Selph, Jeffrey L.,Rigdon, Greg C.,Orr, G. Faye,Davis, Ronda G.,Cooper, Barrett R.,Styles, Virgil L.,Thompson, James B.,Hall, William R.
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p. 399 - 408
(2007/10/03)
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- Fluorescence resonance energy transfer (FRET) as a high-throughput assay for coupling reactions. Arylation of amines as a case study
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A solution-phase assay based on fluorescence resonance energy transfer (FRET) was developed for high-throughput screening of palladium catalyzed aminations of aryl halides. Dansylpiperazine was used as the fluorescent component and a chloro- or bromoarene tagged with an azodye as the quenching partner. Fluorescence intensities of reaction aliquots correlated linearly with reaction yield after dilution to appropriate concentrations. A library of 119 phosphine and heterocyclic carbene ligands was evaluated in duplicate reactions of two combinations. In general, the FRET assay displayed excellent reproducibility, with less than 5% of the duplicate experiments showing significant variability in yields. Among reactions producing greater than 50% yield, the average percent uncertainty was just 5%. For a small subset of sterically hindered ligands, differences in yields between 10 and 20% were observed between the substrates bearing dyes for the FRET assay and substrates that are unfunctionalized. However, the remaining catalyst combinations gave yields similar to those expected from literature precedent. In addition to an evaluation of the accuracy of the FRET assay, this work includes the use of the FRET assay to investigate relative activities of various catalysts for the amination of aryl bromides and chlorides and to find conditions for aminations in more polar solvents. Reactions with K3PO4 base in aqueous mixtures of polar and nonpolar organic solvents were shown to be appropriate for the amination chemistry.
- Stauffer, Shaun R.,Hartwig, John F.
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p. 6977 - 6985
(2007/10/03)
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- Syntheses with organoboranes. XIII. Synthesis of ω-(4-bromophenyl)alkanoic acids and their borylation
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ω-(4-Bromophenyl)alkanoic acids 2c-e were obtained from 1-bromo-4-alkenylbenzenes 5c-e by hydroboration-thermal isomerization-oxidation. Their esters 11c-e were transformed in good yields into the corresponding boronates 12c-e by the cross-coupling reaction with (10) in an ionic liquid, [bmim][BF4]. The use of pinacolborane for the coupling reaction in the ionic liquid gave debromination products, and low yields of 12c-e. Ethyl 3-(4-bromophenyl)propanoate (7c) was transformed into ethyl 3-(4-[1,3,2]dioxaborolanyl)propanoate (9c) by the cross-coupling with [2,2′]bi[[1,3,2]dioxaborinanyl].
- Zaidlewicz, Marek,Wolan, Andrzej
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p. 129 - 135
(2007/10/03)
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- Indenyl compounds for the polymerization of olefins
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Indenyl compound of formula (1) wherein: M is a transition metal from the lanthanides or from group 3, 4, 5 or 6 of the Periodic System of Elements, Q is an anionic ligand to M, k is the number of Q groups, R is a bridging group and Z and X are substituents, wherein R contains at least one sp2-hybridized carbon atom that is bonded to the indenyl group at the 2-position with the exclusion of Ti(deshydronorbiphenacene) dichloride.
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- 6-phenyl-pyridin-2-ylamine derivatives
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The present invention relates to certain 6-phenyl-pyridin-2-ylamine derivatives that exhibit activity as nitric oxide synthase (NOS) inhibitors, to pharmaceutical compositions containing them and to their use in the treatment and prevention of central nervous system disorders.
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- Amine compounds, their production and use
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The present invention provides a compound of the formula: wherein Ar represents an aromatic group which may be substituted; X represents methylene, S, SO, SO2or CO; Y represents a spacer having a main chain of 2 to 5 atoms; n represents an integer of 1 to 5; i) R1and R2each represents a hydrogen atom or a lower alkyl which may be substituted, ii) R1and R2form, taken together with the adjacent nitrogen atom, a nitrogen-containing heterocyclic ring which may be substituted, or iii) R1or R2together with —(CH2)n—N═ form, bonded to a component atom of Ring B, a spiro-ring which may be substituted; Ring A represents an aromatic ring which may be substituted; Ring B represents a 4- to 7-membered nitrogen-containing non-aromatic ring which may be further substituted by alkyl or acyl, with a proviso that X represents S, SO, SO2or CO when Ring A has as a substituent a group represented by the formula: —NHCOR11 where R11represents alkyl, alkoxyalkyl, alkylthioalkyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl or a group represented by the formula: —NHR12 where R12represents alkyl, cycloalkyl, cycloalkylalkyl, aryl or arylalkyl, or a salt thereof; which has an excellent somatostatin receptor binding inhibition action.
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- The effect of vinyl esters on the enantioselectivity of the lipase-catalysed transesterification of alcohols
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The enantioselectivity of the lipase from Pseudomonas cepacia (PCL) in the transesterification of 2-phenyl-1-propanol 1 was studied using a series of vinyl 3-arylpropanoates as acyl donors. The most enantioselective transesterification reaction of the alcohol was attained by using vinyl 3-(p-iodophenyl)- or 3-(p-trifluoromethylphenyl)propanoates, with enantiomer ratios, E, of 116 and 138, respectively. Vinyl 3-phenylpropanoate was also effective for the resolution of 1 mediated by lipases from P. fluorescens and porcine pancreas and for the PCL-catalysed transesterification of several 2-phenyl-1-alkanols. The enantiomeric resolution of 1 was practically carried out by the first enantioselective transesterification using PCL and vinyl 3-(p-iodophenyl)propanoate to afford (R)-1 and then the enantioselective hydrolysis of the resultant ester to afford (S)-1.
- Kawasaki, Masashi,Goto, Michimasa,Kawabata, Shigeki,Kometani, Tadashi
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p. 585 - 596
(2007/10/03)
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- 2-AMINOINDANS AS SELECTIVE DOPAMINE D3 LIGANDS
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Compounds and their pharmaceutically acceptable salts suitable for treating central nervous system disorders associated with the dopamine D3 receptor activity of Formula I: wherein R 1 and R 2 are independently H, C 1-8 alkyl or C 1-8 alkylAryl; X is CH 2 R. sub.3 or NHSO 2 R 4 ; Y is hydrogen, CH 2 R 3, NHSO. sub. 2 R 4, CONR 1 R 2, SO 2 NR 1 R 2, SO 2 CH. sub.3, halogen, OSO 2 CF 3, SCH 3 or OCH 3 ; R 3 is NHSO 2 R 4, SO 2 R 4, CONR 1 R 2 or Aryl; and R. sub.4 is NR 1 R 2, C 1-C 8 alkyl, Aryl or C 1-C. sub.8 alkylAryl.
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- Reduction of olefins on solid support using diimide
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The reduction of solid supported olefinic substrate using diimide is described. The diimide, prepared from sulfonylhydrazide, was found to efficiently reduce the olefinic substrates. Typically, the reaction proceeds in over 90% yield to afford the reduction product cleanly after cleavage from the Wang resin.
- Lacombe, Patrick,Castagner, Bastien,Gareau, Yves,Ruel, Rejean
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p. 6785 - 6786
(2007/10/03)
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- Radiohalogenated for proteins
-
Haloaryl compounds bearing a defined functional group or precursor are metalated with either Sn(n-Bu)3 or SnMe3. The resulting aryltin compound may be transmetalated in site-specific reaction with one of the following organometallic
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- Synthesis of Biological Markers in Fossil Fuels. 2. Synthesis and 13C NMR Studies of Substituted Indans and Tetralins
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Unambiguous syntheses of all possible methyl, ethyl, n-propyl, and n-butyl derivatives of indan and tetralin were developed using the Kumada coupling procedure involving the reaction of aryl or vinyl halides with Grignard reagents in the presence of nickel(II) chloride.An analysis of the 13C NMR spectra of these compounds was also completed.
- Adamczyk, Maciej,Watt, David S.,Netzel, Daniel A.
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p. 4226 - 4237
(2007/10/02)
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- Use of Potassium Bromate: Bromination of Derivatives of Benzene
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Bromination of various derivatives of benzene using potassium bromate under acidic condition has been discussed.
- Banerjee, Amalendu,Banerjee, Gopal Chandra,Adak, Mohini Mohan,Banerjee, Santa,Samaddar, Haraprasad
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p. 985 - 988
(2007/10/02)
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- The Transmission of Substituent-Induced 13C NMR Chemical Shifts in para-Substituted 3-Phenyl Propanoic Acid Methyl Esters
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Carbon-13 chemical shifts have been measured of para-substituted 3-phenyl propanoic acid methyl esters.The substituent-induced 13C shifts of the side chain were related to Hammett substituent effects by the dual substituent parameter method.The transmission of substituent effects and the factors that influence 13C shifts are discussed. - Keywords: Dual Substituent Parameters, Polar and Steric Interactions, Conformational Energy, 13C NMR Spectra
- Radeglia, R.,Spassov, S. L.,Stefanova, R.,Simova, S. D.
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p. 934 - 936
(2007/10/02)
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