- Ligand-Enabled Copper-Catalyzed N-Alkynylation of Sulfonamide with Alkynyl Benziodoxolone: Synthesis of Amino Acid-Derived Ynamide
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Ynamides are versatile building blocks in organic synthesis. However, the synthesis of amino acid-derived ynamides is difficult but in high demand. Herein, we disclose the copper-catalyzed Csp-N coupling of sulfonamide, including amino acid and peptide derivatives, to give ynamides by using alkynyl benziodoxolones with broad functional group tolerance under mild reaction conditions. The electron-rich bipyridine as a ligand and ethanol as solvent were used for the success of this reaction. The usefulness of the obtained amino acid-derived ynamide as building block was showcased by further derivatization to unique amino acid derivatives. A control experiment to elucidate the mechanistic insight was also described.
- Takai, Ryogo,Shimbo, Daisuke,Tada, Norihiro,Itoh, Akichika
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p. 4699 - 4713
(2021/04/06)
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- Synthesis process method of 3-substituted-1H-pyrrole
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The invention provides a synthetic process method of a 3-substituted-1H-pyrrole compound. The process method comprises the following steps: by taking diethylamine hydrochloride and glycine ethyl esterhydrochloride as initial raw materials, respectively carrying out Mannich reaction and sulfamide reaction, and carrying out cyclization reaction, dehydration thinning reaction, aromatization reactionand hydrolysis decarboxylation reaction to obtain a 3-substituted-1H-pyrrole compound. According to the synthesis process method of the 3-substituted-1H-pyrrole compound, the whole synthesis route isgood in step repeatability, mild in operation condition and high in safety, and large-scale production and industrial popularization are facilitated; post-treatment energy consumption is low, a largeamount of toxic wastewater is not generated, no pollution is caused to the environment, the production safety level and the production cost are reduced, application of green and environment-friendlyindustrial production is facilitated, and wide application prospects are achieved.
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Paragraph 0127-0133
(2020/05/30)
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- 1,7-naphthyridine derivative, preparation method and applications thereof
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The present invention relates to a compound represented by a formula (I) or a tautomer, an optical isomer, a nitrogen oxide, a solvate, a pharmaceutically acceptable salt or a prodrug thereof, a preparation method of the compound, a pharmaceutical composi
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Paragraph 0166; 0167; 0168; 0169
(2020/03/23)
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- Three-Component Ring-Opening Reactions of Cyclic Ethers, α-Diazo Esters, and Weak Nucleophiles under Metal-Free Conditions
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A protocol for three-component reactions of cyclic ethers, α-diazo esters, and weak nitrogen, oxygen, carbon, and sulfur nucleophiles (pKa = 2.2-14.8) to afford a variety of structurally complex α-oxyalkylated esters is reported. These reactions involve intermolecular activation of the cyclic ether (present in excess) by the α-diazo ester to form an oxonium ylide under metal-free conditions, followed by ring opening by the nucleophile.
- Lu, Lin,Chen, Chuwei,Jiang, Huanfeng,Yin, Biaolin
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p. 14385 - 14395
(2018/11/27)
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- A α-cycloalanine on the preparation method
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The invention relates to a method for synthesizing alpha-cycloalanine. The method comprises the steps of performing esterification on glycine serving as a raw material, synthesizing esterified product from the former step with p-benzene sulfonyl chloride, performing alkylation reaction on the synthesized product from the former step and 1,2-dibromoethane, and finally hydrolyzing to obtain a product. The method has the advantages of low process pollution, high yield, good purity, low cost and the like, is simple to operate and is a process suitable for industrialized production.
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Paragraph 0015; 0020-0022
(2017/04/29)
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- Base-catalyzed N -N bond cleavage of hydrazones: Synthesis of α-amino ketones
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An efficient Cs2CO3-promoted synthesis of α-amino ketones using hydrazines, aldehydes, and α-haloketones as starting materials through a cascade condensation/nucleophilic substitution/N -N bond cleavage route is developed. The carbonyl group plays a key role in this novel N -N bond cleavage process. Breaking good: A novel method of base-catalyzed N -N bond cleavage of hydrazones has been discovered. A variety of α-amino ketones was synthesized using hydrazines, α-haloketones, and benzaldehyde as starting materials through a cascade condensation/ nucleophilic substitution/N -N bond cleavage sequence.
- Tang, Hai-Tao,Zhou, Yun-Bing,Zhu, Yu,Sun, Hong-Chao,Lin, Min,Zhan, Zhuang-Ping
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p. 1278 - 1281
(2014/05/06)
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- Modular preparation of diverse dipyrrolemethanes
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A modular synthesis of polyfunctional dipyrrolemethanes is presented. Diverse side chains are introduced to 2-carboxypyrrole building blocks in two to four steps, resulting in a collection of substituted pyrroles that, when condensed in one step, give ris
- Pham, Cindy C.,Park, Michelle H.,Pham, Jenny Y.,Martin, Sadie G.,Schramm, Michael P.
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p. 1165 - 1173
(2013/06/05)
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- HETEROCYCLIC INHIBITORS OF NECROPTOSIS
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The invention features a series of heterocyclic derivatives that inhibit tumor necrosis factor alpha (TNF-α) induced necroptosis. The heterocyclic compounds of the invention are described by Formulas (I) and (Ia)-(Ie) and are shown to inhibit TNF-α induce
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Page/Page column 36
(2009/04/25)
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- Dicobalt hexacarbonyl complexes of alkynyl imines in a sequential Staudinger/Pauson-Khand process. A route to new fused tricyclic β-lactams
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(Chemical Equation Presented) Dicobalt hexacarbonyl complexes of alkynyl imines were allowed to react with ketenes via Staudinger reaction. Sequential [2 + 2] cycloaddition/Pauson-Khand reaction led to structurally new fused-tricyclic β-lactams and fused-
- Olier, Clarisse,Azzi, Nadia,Gil, Gerard,Gastaldi, Stephane,Bertrand, Michele P.
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supporting information; experimental part
p. 8469 - 8473
(2009/04/11)
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- Structure-activity relationship and liver microsome stability studies of pyrrole necroptosis inhibitors
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Necroptosis is a regulated caspase-independent cell death pathway resulting in morphology reminiscent of passive non-regulated necrosis. Several diverse structure classes of necroptosis inhibitors have been reported to date, including a series of [1,2,3]thiadiazole benzylamide derivatives. However, initial evaluation of mouse liver microsome stability indicated that this series of compounds was rapidly degraded. A structure-activity relationship (SAR) study of the [1,2,3]thiadiazole benzylamide series revealed that increased mouse liver microsome stability and increased necroptosis inhibitory activity could be accomplished by replacement of the 4-cyclopropyl-[1,2,3]thiadiazole with a 5-cyano-1-methylpyrrole. In addition, the SAR and the cellular activity profiles, utilizing different cell types and necroptosis-inducing stimuli, of representative [1,2,3]thiadiazole and pyrrole derivatives were very similar suggesting that the two compound series inhibit necroptosis in the same manner.
- Teng, Xin,Keys, Heather,Yuan, Junying,Degterev, Alexei,Cuny, Gregory D.
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body text
p. 3219 - 3223
(2009/04/06)
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- Tandem intramolecular hydroalkoxylation-hydroarylation reactions: Synthesis of enantiopure benzofused cyclic ethers from the chiral pool
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A highly efficient and general method for the diastereoselective synthesis of benzo-fused eight-membered carbo- and heterocycles was studied. The method is based on a new tandem gold- or platinum catalyzed hydroalkoxytion- hydroarylation reaction. The use
- Barluenga, Jose,Fernandez, Amadeo,Satrustegui, Amava,Dieguez, Alejandro,Rodriguez, Felix,Fananas, Francisco J.
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supporting information; experimental part
p. 4153 - 4156
(2009/05/07)
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- Pyrrole and pyrazole DAAO inhibitors
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Methods for increasing D-Serine concentration and reducing concentration of the toxic products of D-Serine oxidation, for enhancing learning, memory and/or cognition, or for treating schizophrenia, Alzheimer's disease, ataxia or neuropathic pain, or preventing loss in neuronal function characteristic of neurodegenerative diseases involve administering to a subject in need of treatment a therapeutically effective amount of a compound of formula I, or a pharmaceutically acceptable salt or solvate thereof: wherein R1 and R2 are independently selected from hydrogen, halo, nitro, alkyl, acyl, alkylaryl, and XYR5; or R1 and R2, taken together, form a 5, 6, 7 or 8-membered substituted or unsubstituted carbocyclic or heterocyclic group; X and Y are independently selected from O, S, NH, and (CR6R7)n; R3 is hydrogen, alkyl or M+; M is aluminum, calcium, lithium, magnesium, potassium, sodium, zinc ion or a mixture thereof; Z is N or CR4; R4 is from selected from hydrogen, halo, nitro, alkyl, alkylaryl, and XYR5; R5 is selected from aryl, substituted aryl, heteroaryl and substituted heteroaryl; R6 and R7 are independently selected from hydrogen and alkyl; n is an integer from 1 to 6; at least one of R1, R2 and R4 is other than hydrogen; and at least one of X and Y is (CR6R7)n. D-serine or cycloserine may be coadministered along with the compound of formula I.
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Page/Page column 6; 39-40
(2008/06/13)
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- Regioselectivity and the nature of the reaction mechanism in nucleophilic substitution reactions of 2,4-dinitrophenyl X-substituted benzenesulfonates with primary amines
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Second-order rate constants have been measured for the reaction of 2,4-dinitrophenyl X-substituted benzenesulfonates with a series of primary amines. The nucleophilic substitution reaction proceeds through competitive S-O and C-O bond fission pathways. The S-O bond fission occurs dominantly for reactions with highly basic amines or with substrates having a strong electron-withdrawing group in the sulfonyl moiety. On the other hand, the C-O bond fission occurs considerably for the reactions with low basic amines or with substrates having a strong electron-donating group in the sulfonyl moiety, emphasizing that the regioselectivity is governed by both the amine basicity and the electronic effect of the sulfonyl substituent X. The apparent second-order rate constants for the S-O bond fission have resulted in a nonlinear Bronsted-type plot for the reaction of 2,4-dinitrophenyl benzenesulfonate with 10 different primary amines, suggesting that a change in the rate-determining step occurs upon changing the amine basicity. The microscopic rate constants (k1 and k2/k-1 ratio) associated with the S-O bond fission pathway support the proposed mechanism. The second-order rate constants for the S-O bond fission result in good linear Yukawa-Tsuno plots for the aminolyses of 2,4-dinitrophenyl X-substituted benzenesulfonates. However, the second-order rate constants for the C-O bond fission show no correlation with the electronic nature of the sulfonyl substituent X, indicating that the C-O bond fission proceeds through an SNAR mechanism in which the leaving group departure occurs rapidly after the rate-determining step.
- Um, Ik-Hwan,Hong, Jin-Young,Kim, Jung-Joo,Chae, Ok-Mi,Bae, Sun-Kun
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p. 5180 - 5185
(2007/10/03)
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- Unexpected alkoxyl migration in the reaction of silyl ketene acetals with p-toluenesulfonyl azide
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The reaction of p-toluenesulfonyl azides with several silyl ketene acetals has been investigated. 1-Trimethylsilyloxy-ethylene reacted with TsN3 to give a good yield of N-p-toluenesulfonyl substituted glycinates exclusively. However, during the reaction of 1-trimethylsilyloxy-propene with TsN3, an unexpected alkoxyl migration occurred to give N-acylsulfonyl amides; other products, N-p-toluenesulfonyl substituted aziridines were also obtained. In the case of dialkyl substituted silyl ketene acetals, three products were formed, i.e. aziridines, α-amino esters, and N-acylsulfonyl amides. The mechanism for the alkoxyl migration was discussed.
- Xu, Yong,Zhu, Shizheng
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p. 3909 - 3913
(2007/10/03)
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- Chemoselective reduction of α-imino carbonyl compounds into α-amino carbonyl compounds with titanium tetraiodide
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α-Imino carbonyl compounds are chemoselectively reduced with titanium tetraiodide to give α-amino carbonyl compounds in good to excellent yields.
- Shimizu, Makoto,Sahara, Tetsuya,Hayakawa, Ryuuichirou
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p. 792 - 793
(2007/10/03)
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- Oxidation-induced Acyl group transfer from hydroquinone esters to nucleophiles
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Bivalent oxidation of 3,5-di-tert-butyl-hydroquinone monoesters leads to phenoxenium ions, which can transfer an acyl group to nucleophiles. Based on this principle, dipeptides, glyco-amino acids and N-sulfonyl-amino acids were synthesized from hydroquino
- Reischl, Gerald,El-Mobayed, Medhat,Bei?wenger, Rudolf,Regier, Klaus,Maichle-M?ssmer, C?cilia,Rieker, Anton
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p. 765 - 773
(2007/10/03)
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- Synthesis of new organothiophosphorus insectoacaricides containing N-acylated amino acid fragments
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Methods for the synthesis of O-alkyl S-(N-acyl-N-alkoxycarbonylalkyl)aminomethyl (methyl)thio- and -dithiophosphonates based on the reaction between alkaline-metal salts of O-alkyl (methyl)thio- and -dithiophosphonoates and N-alkoxycarbonyl-N-chloromethyl
- Shipov, A. E.,Genkina, G. K.,Zhdanova, G. V.,Petrovskii, P. V.,Roslavtseva, S. A.,et al.
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p. 1231 - 1238
(2007/10/02)
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- An Improved Synthesis of Pyrroles from N-p-Toluenesulfonylglycine Esters and α,β-Unsaturated Aldehydes and Ketones
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N-p-Toluenesulfonylglycine esters 2 condensed with α,β-unsaturated carbonyl compounds 1 in the presence of the non-nucleophilic base DBU to give hydroxypyrrolidines 3.Dehydration with phosphorous oxychloride-pyridine, followed by DBU mediated elimination
- Lash, Timothy D.,Hoehner, Michael C.
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p. 1671 - 1676
(2007/10/02)
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- Sulfonyl transfer from imidazoles
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The rate constants for the non-catalyzed bimolecular substitution of 1-tosylimidazole, 1, 1-tosyl-3-methylimidazolium, 2, and 1-tosyl-2,3-dimethylimidazolium, 3, chlorides by primary aliphatic amines (5 n Nu=0.5, 0.5 and 0.6 respectively.Despite large variations in the reactivity, 6 powers of ten from 1 to 2, and in the leaving group pK's, 7 units from 2 to 1, the nucleophile effect is found to be nearly constant.The nucleofuge effect is also independent of the nucleophile; apparent βL-coefficients of approximately - 0.9 are observed whatever the amine.These data correspond to rate-limiting transition states where there is small but significant bonding of the sulfonyl with the entering amines and with the leaving imidazoles.These results strongly suggest a concerted single-step displacement mechanism; however, a stepwise mechanism involving a very unstable and very short-lived pentahedric intermediate cannot be strictly ruled out.These findings are compared with those on other acyl transfers.
- Monjoint, P.,Ruasse, M. F.
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p. 356 - 360
(2007/10/02)
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- NUCLEOPHILIC SUBSTITUTION AT SULFONYL SULFUR ATOM : AMINOLYSIS OF 1-TOSYL-3-METHYL IMIDAZOLIUM CHLORIDE IN AQUEOUS MEDIUM.
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Kinetics of the reaction of 1-tosyl-3-methyl-imidazolium chloride with various amines were measured to examine the nature of sulfonyl transfer in enzymatic reactions.The activations parameters and the value of the Broensted exponent, β=0.48, are consistent with a small degree of bonding between the entering amine and the sulfur atom in the transition state.Similarities in the nucleophilic behavior of sulfonyl and carbonyl groups are detected.
- Monjoint, Pierre,Ruasse, Marie-Francoise
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p. 3183 - 3186
(2007/10/02)
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- A Novel Synthesis of Peptide Based on the Photochemistry of 5-Azido-1,3,4-oxadiazoles
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A novel approach to the synthesis of peptides is described.Various N-protected amino acid hydrazides 17 were converted to the salts 18 by condensation with carbon disulfide in methanolic potassium hydroxide.Thermal cyclization of 18 to the heterocycles 19 was followed by reaction with methyl iodide to yield the sulfides 20.After oxidation of 20 to the corresponding sulfones 21, the title compounds 22 were prepared by treating 21 with sodium azide.Deprotection then yielded the free bases 23.Utilization of 22 and 23 in peptide synthesis, relying on a photochemical degradation of the title heterocycle present in these compounds, is described.The scope and limitations of this new methodology are also discussed.
- Confalone, Pat N.,Woodward, Robert B.
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p. 902 - 906
(2007/10/02)
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- MODELS OF FOLATE COENZYMES-VII SYNTHESIS AND CARBON TRANSFER REACTIONS OF N5,N10-METHENYL AND N5,N10-METHYLENETETRAHYDROFOLATE MODELS
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Carboxylate esters react with 1,2-diaminoethanes to yield imidazolines, which upon consecutive reaction with acetic anhydride or tosyl chloride and methyl iodide give imidazolinium salts that serve as models of N5,N10-(CH+)-tetrahydrofolate (THF) coenzymes (7a,b and 18a,b).Reduction of the latter salts with sodium borohydride or reaction with anions (R-) give the corresponding 5,10--THF models.Mono- and bifunctional nucleophiles react with 18a,b to yield carbon-transfer products. 6-Alkylamino-1,3-dimethyluracils react with 1-tosyl-3,4,4-trimethylimidazolidine (the reduction product of 18b), in the presence of acetic acid, to form carbon-transfer products via a mechanism which bears close analogy to the mechanism of action of thymidylate synthetase.
- Bieraeugel, H.,Plemp, R.,Hiemstra, H. C.,Pandit, U. K.
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p. 3971 - 3980
(2007/10/02)
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