- Graphene Oxide: A Metal-Free Carbocatalyst for the Synthesis of Diverse Amides under Solvent-Free Conditions
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An environmentally friendly, inexpensive, carbocatalyst, graphene oxide (GO) promoted efficient, metal-free transamidation of various carboxamides with aliphatic, cyclic, and aromatic amines is demonstrated. The protocol is equally applicable to phthalimide, urea, and thioamide determining its adaptability. The oxygenated functionalities such as carbonyl (?C=O), epoxy (?O?), carboxyl (?COOH) and hydroxyl (?OH), present on graphene oxide surface impart acidic properties to the catalyst. The graphene oxide being heterogeneous in nature, work efficiently under solvent-free reaction conditions providing desired products in good to excellent yields. The one-pot synthesis of 2,3-Dihydro-5H-benzo[b]-1,4-thiazepin-4-one moiety by GO catalyzed Aza Michael addition followed by intramolecular transamidation is also described. A plausible reaction mechanistic pathway involving H-bonding is discussed. The graphene oxide can be recycled and reused up to five cycles without much loss in catalytic activity. (Figure presented.).
- Patel, Khushbu P.,Gayakwad, Eknath M.,Patil, Vilas V.,Shankarling, Ganapati S.
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supporting information
p. 2107 - 2116
(2019/03/26)
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- Visible-Light-Mediated Efficient Metal-Free Catalyst for α-Oxygenation of Tertiary Amines to Amides
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A metal-free system has been discovered for the efficient α-oxygenation of tertiary amines to the corresponding amides using oxygen as an oxidant. This visible-light-mediated oxygenation reaction exhibited excellent substrates scope under mild reaction conditions and generated water as the only byproduct. The synthetic utility of this approach has been demonstrated by applying onto drug molecules. At the end, detailed mechanistic reactions clearly showed the role of oxygen and the photocatalyst.
- Zhang, Yu,Riemer, Daniel,Schilling, Waldemar,Kollmann, Jiri,Das, Shoubhik
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p. 6659 - 6664
(2018/06/25)
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- Alkoxide-Catalyzed Hydrosilylation of Cyclic Imides to Isoquinolines via Tandem Reduction and Rearrangement
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An alkoxide-catalyzed hydrosilylation of cyclic imides to isoquinolines was realized via tandem reduction and rearrangement. Using TMSOK as the catalyst and (EtO)2MeSiH as the reductant, a series of cyclic imides containing different functional groups were reduced to the corresponding 3-aryl isoquinolines in moderate to good yields. The scenario of the reaction pathway was supposed to involve the reduction of imides to ω-hydroxylactams, which underwent rearrangement in the presence of a base catalyst, and then the carbonyl reduction, followed by siloxy elimination.
- Wu, Xiaoyu,Ding, Guangni,Yang, Liqun,Lu, Wenkui,Li, Wanfang,Zhang, Zhaoguo,Xie, Xiaomin
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supporting information
p. 5610 - 5613
(2018/09/12)
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- MANGANESE BASED COMPLEXES AND USES THEREOF FOR HOMOGENEOUS CATALYSIS
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The present invention relates to novel manganese complexes and their use, inter alia, for homogeneous catalysis in (1) the preparation of imine by dehydrogenative coupling of an alcohol and amine; (2) C-C coupling in Michael addition reaction using nitriles as Michael donors; (3) dehydrogenative coupling of alcohols to give esters and hydrogen gas (4) hydrogenation of esters to form alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di- lactones), or polyesters); (5) hydrogenation of amides (including cyclic dipeptides, lactams, diamide, polypeptides and polyamides) to alcohols and amines (or diamine); (6) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (7) dehydrogenation of secondary alcohols to ketones; (8) amidation of esters (i.e., synthesis of amides from esters and amines); (9) acylation of alcohols using esters; (10) coupling of alcohols with water and a base to form carboxylic acids; and (11) preparation of amino acids or their salts by coupling of amino alcohols with water and a base. (12) preparation of amides (including formamides, cyclic dipeptides, diamide, lactams, polypeptides and polyamides) by dehydrogenative coupling of alcohols and amines; (13) preparation of imides from diols.
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Paragraph 00395
(2017/09/05)
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- COMPOSITIONS FOR PROMOTING READTHROUGH OF PREMATURE TERMINATION CODONS, AND METHODS OF USING THE SAME
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Disclosed are compounds of general formula (I) that promote readthrough of a premature termination codon (PTC) of an RNA molecule in a translation system, and their use, alone or in combination with other compounds, such as aminoglycoside, to treat diseases or disorders ameliorated by modulation of a premature termination codon (PTC) of an RNA molecule in a translation system. The disorder or disease may be Dystrophic epidermolysis bullosa, Batten disease, Duchenne muscular dystrophy, cancer, and spinal muscular atrophy. Ar-L-B (I)
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Page/Page column 213; 214; 215; 216; 217; 229
(2017/04/11)
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- Synthetic method of astemizole drug intermediate N-(4-fluorobenzyl)phthalimide
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A synthetic method of astemizole drug intermediate N-(4-fluorobenzyl)phthalimide comprises the following steps: adding 0.21mol of stannous chloride, 230ml of nitromethane and 0.51mol of N-aminomethylphthalimide to a reaction container provided with a stirrer, a thermometer, a reflux condenser and a dropping funnel, controlling the stirring speed to be 130-170rpm, heating the obtained solution to 60-65DEG C, maintaining refluxing for 3-4h, adding 0.71-0.73mol of fluorobenzene, heating to 70-75DEG C after fluorobenzene addition is finished, reacting for 19-21h, cooling the solution to 10-15DEG C, adding 230ml of a potassium chloride solution and 90ml of an oxalic acid solution, maintaining the stirring speed at 140-160rpm for 90-120min, precipitating a solid, carrying out pumping filtration, washing the obtained solid with a salt solution, dehydrating through a dehydrating agent, washing the dehydrated solid with cyclohexane, and recrystallizing the washed solid in acetonitrile to obtain a white crystal N-(4-fluorobenzyl)phthalimide.
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Paragraph 0013; 0014
(2016/11/09)
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- Transamidation catalysed by a magnetically separable Fe3O4 nano catalyst under solvent-free conditions
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An environmentally benign protocol for transamidation of carboxamides with different amines under solvent free conditions using magnetically separable nano Fe3O4 as a heterogeneous catalyst is developed. The series of aryl and alkyl amines with long chain alkyl substituents have been selectively converted into transamide products. The current protocol offers a diverse substrate scope with good yield of the product. The Fe3O4 nano catalyst has also been used for formylation of amines via transamidation of dimethyl formamide. Efficient transamidation, ease of work up, simple separation and reusability of the catalyst for up to six runs are the important highlights of this process.
- Thale, Pranila B.,Borase, Pravin N.,Shankarling, Ganapati S.
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p. 52724 - 52728
(2016/06/14)
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- Cuprous Oxide Catalyzed Oxidative C-C Bond Cleavage for C-N Bond Formation: Synthesis of Cyclic Imides from Ketones and Amines
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Selective oxidative cleavage of a C-C bond offers a straightforward method to functionalize organic skeletons. Reported herein is the oxidative C-C bond cleavage of ketone for C-N bond formation over a cuprous oxide catalyst with molecular oxygen as the oxidant. A wide range of ketones and amines are converted into cyclic imides with moderate to excellent yields. In-depth studies show that both α-C-H and β-C-H bonds adjacent to the carbonyl groups are indispensable for the C-C bond cleavage. DFT calculations indicate the reaction is initiated with the oxidation of the α-C-H bond. Amines lower the activation energy of the C-C bond cleavage, and thus promote the reaction. New insight into the C-C bond cleavage mechanism is presented.
- Wang, Min,Lu, Jianmin,Ma, Jiping,Zhang, Zhe,Wang, Feng
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supporting information
p. 14061 - 14065
(2016/01/25)
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- A phthalimidation protocol that follows protein defined parameters
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This work outlines the first phthalimidation protocol suitable for protein labeling and performed in aqueous media at room temperature and neutral pH with no catalyst or co-reagent required. The methodology is suitable for a range of amines and its efficiency was determined with chemoselective and site-selective protein labeling. This journal is
- Singudas, Rohith,Adusumalli, Srinivasa Rao,Joshi, Pralhad Namdev,Rai, Vishal
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supporting information
p. 473 - 476
(2015/01/09)
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- Efficient conversion of acids and esters to amides and transamidation of primary amides using OSU-6
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OSU-6, an MCM-41 type hexagonal mesoporous silica with strong Bronsted acid properties, has been used to promote the high-yield conversion of carboxylic acids and esters to carboxamides as well as transamidations of primary amides in a one-pot solventless approach. A metal-free heterogeneous catalyst that promotes all of these processes has not been previously reported. OSU-6 enables these transformations to proceed in shorter times and at lower temperatures for a broad range of substrates. An added benefit is that the catalyst can be recycled and reused multiple times without significant loss of activity.
- Nammalwar, Baskar,Muddala, Nagendra Prasad,Watts, Field M.,Bunce, Richard A.
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p. 9101 - 9111
(2015/11/09)
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- Structure-based design of phthalimide derivatives as potential cyclooxygenase-2 (COX-2) inhibitors: Anti-inflammatory and analgesic activities
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A group of 30 cyclic imides (1-10a-c) was designed for evaluation as a selective COX-2 inhibitor and investigated in vivo for anti-inflammatory and analgesic activities. Compounds 6a, 6b, 7a and 7b exhibit optimal COX-2 inhibitory potency (IC50 Combining double low line 0.18, 0.24, 0.28 and 0.36 μM; respectively) and selectivity index (SI) range of 363-668. In vitro COX-1/COX-2 inhibition structure-activity studies identified compound 6a as a highly potent (IC50 Combining double low line 0.18 μM), and an extremely selective [COX-2 (SI) Combining double low line 668] comparable to celecoxib [COX-2 (SI) > 384], COX-2 inhibitor that showed superior anti-inflammatory activity (ED50 Combining double low line 54.0 mg/kg) relative to diclofenac (ED50 Combining double low line 114 mg/kg). Molecular Docking study of the synthesized compound 6a into the active site of COX-2 revealed a similar binding mode to SC-558, a selective COX-2 inhibitor. Docking study showed that the methoxy moeities of 6a inserted deep inside the 2°-pocket of the COX-2 active site, where the O-atoms of such groups underwent an H-bonding interaction with His90 (3.02 g.,), Arg513 (1.94, 2.83 g.,), and Gln192 (3.25 g.,).
- Alanazi, Amer M.,El-Azab, Adel S.,Al-Suwaidan, Ibrahim A.,Eltahir, Kamal Eldin H.,Asiri, Yousif A.,Abdel-Aziz, Naglaa I.,Abdel-Aziz, Alaa A.-M.
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p. 115 - 123
(2015/02/19)
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- An unprecedented approach to the Gabriel amine synthesis utilizing tosylhydrazones as alkylating agents
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A new and one-pot version of the Gabriel phthalimide amine synthesis utilizing carbonyl compounds as alkylating agents via their tosylhydrazone surrogates is disclosed. The alkylation involves copper catalysed carbene insertion into the N-H bond of phthalimide. Basically, the protocol also offers a powerful tool for deoxygenative hydroamination of carbonyl compounds.
- Yadav, Arvind K.,Yadav, Lal Dhar S.
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p. 34764 - 34767
(2014/11/08)
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- Palladium-catalyzed carbonylative synthesis of phthalimides from 1,2-dibromoarenes with molybdenum hexacarbonyl as carbon monoxide source
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We describe here a convenient and mild, carbon monoxide gas-free palladium-catalyzed procedure to obtain N-substituted phthalimides with molybdenum hexacarbonyl as carbon monoxide precursor. These conditions tolerate a number of functional groups on the benzene ring as well as a number of amines and give the corresponding phthalimides in good to excellent yields. Copyright
- Wu, Xiao-Feng,Oschatz, Stefan,Sharif, Muhammad,Flader, Anika,Krey, Lisa,Beller, Matthias,Langer, Peter
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supporting information
p. 3581 - 3585
(2014/01/06)
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- Substituted Dihydroisoindolones As Allosteric Modulators of Glucokinase
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The present invention relates to compounds of Formula (I), methods for preparing these compounds, compositions, intermediates and derivatives thereof and for treating glucokinase mediated disorders. More particularly, the compounds of the present invention are glucokinase modulators useful for treating disorders including, but not limited to, type II diabetes.
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Page/Page column 32
(2010/11/27)
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- Fluorous Mitsunobu reagents and reactions
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A fully fluorous Mitsunobu reaction procedure is introduced. This employs both existing [(C6F13CH2CH2C6H 4)2PPh] and new [C8F17CH2CH2C6H 4PPh2] fluorous phosphines and a new fluorous azodicarboxylate (C6F13CH2CH2OC(O)N=NCOOCH 2CH2C6F13). A procedure involving parallel reactions with representative nucleophiles and alcohols under typical Mitsunobu conditions in THF followed by rapid solid phase extraction (spe) over fluorous silica provides clean products in excellent yields. The fluorous fraction containing the oxidized phosphine oxide and the reduced hydrazide can be readily separated and the starting reagents can be regenerated by appropriate redox reactions in high yield for reuse.
- Dandapani, Sivaraman,Curran, Dennis P.
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p. 3855 - 3864
(2007/10/03)
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- Superelectrophilic Tscherniac amidomethylation of aromatics with N-hydroxymethylphthalimide in trifluoromethanesulfonic acid
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N-Hydroxymethylphthalimide in trifluoromethanesulfonic acid (triflic acid) reacts readily at room temperature with benzene, halo-, polyhalo- and halonitrobenzenes to give high yields of the corresponding α-amidomethylated products. The scope of the α-amidomethylation reaction is substantially extended by the studied system, which is considered to involve diprotonated N-hydroxymethylphthalimide as the de facto superelectrophilic reagent.
- Olah,Wang,Sandford,Oxyzoglou,Prakash
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p. 1077 - 1079
(2007/10/02)
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