- Dealkoxylation ofN-alkoxyamides without an external reductant driven by Pd/Al cooperative catalysis
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Lewis acid-assisted palladium-catalysed dealkoxylation ofN-alkoxyamides has been developed. This reaction proceeded smoothly with a range ofN-alkoxyamides in the absence of an external reductant, thereby establishing a convenient and reductant-free protocol. In addition, a gram-scale reaction could be achieved. Preliminary mechanistic investigations indicated that β-hydrogen elimination from a palladium alkoxide intermediate generated an intramolecular hydride source.
- Suzuki, Hirotsugu,Shiomi, Takahiro,Yoneoka, Kenji,Matsuda, Takanori
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supporting information
p. 7545 - 7548
(2020/10/15)
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- Direct Copper-Catalyzed Three-Component Synthesis of Sulfonamides
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First introduced into medicines in the 1930s, the sulfonamide functional group continues to be present in a wide range of contemporary pharmaceuticals and agrochemicals. Despite their popularity in the design of modern bioactive molecules, the underpinning methods for sulfonamide synthesis are essentially unchanged since their introduction, and rely on the use of starting materials with preinstalled sulfur-functionality. Herein we report a direct single-step synthesis of sulfonamides that combines two of the largest monomer sets available in discovery chemistry, (hetero)aryl boronic acids and amines, along with sulfur dioxide, using a Cu(II) catalyst, to deliver a broad range of sulfonamides. Sulfur dioxide is provided by the surrogate reagent DABSO. The reaction tolerates broad variation in both coupling partners, including aryl, heteroaryl and alkenyl boronic acids, as well as cyclic and acyclic alkyl secondary amines, and primary anilines. We validate the method by showing that a variety of drugs, and drug-fragments, can be incorporated into the process.
- Chen, Yiding,Murray, Philip R. D.,Davies, Alyn T.,Willis, Michael C.
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supporting information
p. 8781 - 8787
(2018/07/29)
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- Efficient one-stage procedure of Beckmann ketones rearrangement in the presence of hydroxylamine
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Ketoximes formed from ketones in the presence of hydroxylamine and silica gel in formic acid undergo in situ the Beckmann rearrangement under mild conditions affording in high yields the corresponding amides. Unsymmetrical aromatic ketones, methyl aryl ketones, and methyl cyclohexyl ketone under these conditions form as a rule amides mixtures.
- Kuksenok,Shtrykova,Filimonov,Sidel'nikova
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p. 196 - 199
(2016/04/19)
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- Hydrogen Self-Sufficient Arene Reduction to Cyclohexane Derivatives Using a Combination of Platinum on Carbon and 2-Propanol
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Various arenes have been hydrogenated using platinum on carbon in a 2-propanol-aqueous mixed solvent at 100 C without the addition of flammable hydrogen gas to give the corresponding cyclohexane derivatives. 2-Propanol plays a role as an efficient hydrogen source based on the platinum on carbon-catalyzed dehydrogenation.
- Sawama, Yoshinari,Mori, Misato,Yamada, Tsuyoshi,Monguchi, Yasunari,Sajiki, Hironao
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supporting information
p. 3667 - 3670
(2016/01/25)
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- Highly Selective Hydrogenation of Aromatic Ketones and Phenols Enabled by Cyclic (Amino)(alkyl)carbene Rhodium Complexes
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Air-stable Rh complexes ligated by strongly σ-donating cyclic (amino)(alkyl)carbenes (CAACs) show unique catalytic activity for the selective hydrogenation of aromatic ketones and phenols by reducing the aryl groups. The use of CAAC ligands is essential for achieving high selectivity and conversion. This method is characterized by its good compatibility with unsaturated ketones, esters, carboxylic acids, amides, and amino acids and is scalable without detriment to its efficiency.
- Wei, Yu,Rao, Bin,Cong, Xuefeng,Zeng, Xiaoming
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supporting information
p. 9250 - 9253
(2015/08/11)
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- Acid hydrolysis of amides obtained by Beckmann rearrangement of methyl ketones oximes of unsaturated γ-lactone, aromatic, and alicyclic series
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Beckmann rearrangement was performed of oximes of substituted 3-acetyl-4-methyl-5,5-dimethyl(pentamethylene)-2-oxo-2,5-dihydrofuranes in the presence of boron trifluoride etherate. Aiming at establishing the spatial arrangement of the oximes the hydrolysis was carried out of acid amides obtained by Beckmann rearrangement of oximes of methyl ketones belonging to unsaturated γ-lactone series and also to aromatic and alicyclic series. The hydrolysis with 20% sulfuric acid led to the formation of the corresponding acid and amine, and the hydrolysis with acetic and hydrochloric acids resulted in retrobeckmann rearrangement giving the initial oximes.
- Tokmadzhyan
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experimental part
p. 1746 - 1749
(2012/03/10)
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- Selective hydrogenation of amides using Rh/Mo catalysts
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Rh/Mo catalysts formed in situ from Rh6(CO)16 and Mo(CO)6 are effective for the liquid phase hydrogenation of CyCONH2 to CyCH2NH2 in up to 87% selectivity, without the requirement for ammonia to inhibit secondary amine formation. Use of in situ HP-FTIR spectroscopy has shown that decomposition of metal carbonyl precursors occurs during an extended induction period, with the generation of recyclable, heterogeneous, bimetallic catalysts. Variations in Mo:Rh content have revealed significant synergistic effects on catalysis, with optimum performance at values of ca. 0.6, and substantially reduced selectivities at ≥1. Good amide conversions are noted within the reaction condition regimes 50-100 bar H2 and 130-160 °C. Ex situ characterization of the catalysts, using XRD, XPS and EDX-STEM, has provided evidence for intimately mixed (ca. 2-4 nm) particles that contain metallic Rh and reduced Mo oxides, together with MoO3. Silica-supported Rh/Mo analogues, although active, perform poorly at 150 °C and deactivate during recycle.
- Beamson, Graham,Papworth, Adam J.,Philipps, Charles,Smith, Andrew M.,Whyman, Robin
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experimental part
p. 93 - 102
(2010/09/16)
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- Selective hydrogenation of amides using ruthenium/ molybdenum catalysts
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Recyclable, heterogeneous bimetallic ruthenium/molybdenum catalysts, formed in situ from triruthenium dodecacarbonyl [Ru3(CO)12] and molybdenum hexacarbonyl [Mo(CO)6], are effective for the selective liquid phase hydrogenation of cyclohexylcarboxamide (CyCONH2) to cyclohexanemethylamine (CyCH2NH2), with no secondary or tertiary amine by-product formation. Variation of Mo:Ru composition reveals both synergistic and poisoning effects, with the optimum combination of conversion and selectivity at ca. 0.5, and total inhibition of catalysis evident at ≥1. Good amide conversions are noted within the reaction condition regimes 20100 bar hydrogen and 145-160°C. The order of reactivity of these catalysts towards reduction of different amide functional groups is primary > tertiary ? secondary. In situ HP-FT-IR spectroscopy confirms that catalyst genesis occurs during an induction period associated with decomposition of the organometallic precursors. Ex situ characterisation, using XRD, XPS and EDX-STEM, for active Mo:Ru compositions, has provided evidence for intimately mixed ca. 2.5-4 nm particles that contain metallic ruthenium, and molybdenum (in several oxidation states, including zero).
- Beamson, Graham,Papworth, Adam J.,Philipps, Charles,Smith, Andrew M.,Whyman, Robin
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experimental part
p. 869 - 883
(2010/07/05)
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- CALCIUM ION CHANNEL MODULATORS and USES THEREOF
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Compounds of formula (I), wherein R1 is hydrogen, hydroxyl or aralkyl; R2 is an optionally substituted alkyl, aryl or heteroaryl (said substituents are selected from hydroxyl, alkoxyl, haloalkoxyl, aryl, heteroaryl, cycloalkyl, amino, monoalkylamino, dialkylamino, alkylsulphonyl, alkylsulphinyl, alkylsulphonylamino, acylamino, saturated or partially unsaturated heterocyclic groups and groups of formula COY); W is selected from oxygen, sulphur, groups of formula NR7, wherein R7 is hydrogen, alkyl, aryl or heteroaryl and groups of formula CR8R9, wherein R8 and R9 are hydrogen, alkyl, aryl or heteroaryl; and X is selected from nitrogen and groups of formula CR10, wherein R10 is hydrogen, alkyl, aryl, heteroaryl, halogen or haloalkyl, inhibit the interaction between Cavx channels and Cavβ proteins and are of use in the treatment and prevention of a number of diseases and conditions including pain and lower urinary tract disorders.
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Page/Page column 120
(2010/04/27)
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- INDOLE- 3 -GLYOXYLAMIDE DERIVATIVES FOR USE AS CALCIUM ION CHANNEL MODULATORS
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Compounds of formula (I) are of use in treating a range of conditions, including pain.
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Page/Page column 93
(2009/12/05)
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- The ruthenium-catalyzed reduction and reductive N-alkylation of secondary amides with hydrosilanes: Practical synthesis of secondary and tertiary amines by judicious choice of hydrosilanes
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(Chemical Equation Presented) A triruthenium cluster, (μ3, η2,η3,η5-acenaphthylene)Ru 3(CO)7 (1) catalyzes the reaction of secondary amides with hydrosilanes, yielding a mixture of secondary amines, tertiary amines, and silyl enamines. Production of secondary amines with complete selectivity is achieved by the use of higher concentration of the catalyst (3 mol %) and the use of bifunctional hydrosilanes such as 1,1,3,3-tetramethyldisiloxane. Acidic workup of the reaction mixture affords the corresponding ammonium salts, which can be treated with a base, providing a facile method for isolation of secondary amines with high purity. In contrast, tertiary amines are formed with high selectivity by using lower concentration of the catalyst (1 mol %) and polymeric hydrosiloxanes (PMHS) as reducing agent. Reduction with PMHS encapsulates the ruthenium catalyst and organic byproducts to the insoluble silicone resin. The two reaction manifolds are applicable to various secondary amides and are practical in that the procedures provide the desired secondary or tertiary amine as a single product. The product contaminated with only minimal amounts of ruthenium and silicon residues. On the basis of the products and observed side products as well as NMR studies a mechanistic scenario for the reaction is also described.
- Hanada, Shiori,Ishida, Toshiki,Motoyama, Yukihiro,Nagashima, Hideo
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p. 7551 - 7559
(2008/02/12)
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- The extraordinary reactions of phenyldimethylsilyllithium with N,N-disubstituted amides
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The reactions of the silyllithium reagent with tertiary amides was discussed. The enediamines were easily isomerized from cis to trans, easily oxidized to dienediamines and were hydrolyzed to α-aminoketones. If the two equivalents of the silyllithium reagent were used, the product was an α-silylamine. The results show that each member of the homologous series of amides gives rise to a substantially different product.
- Buswell, Marina,Fleming, Ian,Ghosh, Usha,Mack, Stephen,Russell, Matthew,Clark, Barry P.
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p. 3006 - 3017
(2007/10/03)
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- Succinimide derivatives. II. Synthesis and antipsychotic activity of N- [4-[4-(1,2-benzisothiazol-3-yl)-1-piperazinyl]butyl]1,2-cis- cyclohexanedicarboximide (SM-9018) and related compounds
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Cyclic imides bearing ω-(4-benzisothiazol-3-yl-1-piperazinyl)alkyl moieties were synthesized and tested for antipsychotic activity. The in vitro binding affinities of these compounds were examined for dopamine 2 (D2) and serotonin 2 (5-HT2) receptor sites. Structure-activity relationships within these series are discussed. One of these compounds, N-[4-[4-(1,2- benzisothiazol-3-yl)-1-piperazinyl]butyl]-1,2-cis-cyclohexanedicarboximide (SM-9018), was found to be more potent and more selective in vivo than tiospirone in its antipsychotic activity. SM-9018 (17) is currently undergoing clinical evaluation as a selective antipsychotic agent.
- Ishizumi,Kojima,Antoku,Saji,Yoshigi
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p. 2139 - 2151
(2007/10/03)
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- Cationic Carbon to Nitrogen Rearrangements in the Reactions of N-(Sulfonyloxy)amines with Aldehydes
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A series of aromatic and aliphatic aldehydes was reacted with N-((p-nitrobenzenesulfonyl)oxy)methylamine in chloroform.Products resulting from both carbon migration and hydride migration to nitrogen were isolated.The ratios of carbon to hydride migration products were used to clarify the reaction mechanism.The results support a two-step process in which cationic carbon to nitrogen rearrangements is rate determining.
- Hoffman, Robert V.,Salvador, James M.
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p. 4487 - 4490
(2007/10/02)
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- A MILD EFFICIENT PROCEDURE FOR THE CONVERSION OF CARBOXYLIC ACID ESTERS TO PRIMARY AMIDES USING FORMAMIDE/METHANOLIC SODIUM METHOXIDE
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An improved method for the preparation of primary carboxylic acid amides from the corresponding esters is described.This reaction was easily followed by GLC and was usually complete in less than one hour.
- Jagdmann, G. Erik,Munson, H. Randall,Gero, Thomas W.
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p. 1203 - 1208
(2007/10/02)
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- Dodecacarbonyltriruthenium catalyzed one-to-one addition of N-substituted formamides to olefins
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Dodecacarbonyltriruthenium (Ru3(CO)12) showed high catalyitic activity for the first one-to-one addition of N-substituted formamides to both terminal and internal olefins at 180-200 deg C under a carbon monoxide pressure of 20 kg cm-2.The addit
- Tsuji, Yasushi,Yoshii, Seiji,Ohsumi, Tatsuya,Kondo, Teruyuki,Watanabe, Yoshihisa
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p. 379 - 386
(2007/10/02)
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- Preparation of Vicinal N-Alkylamino Alcohols via Acylation-Rearrangement of Nitrones Followed by Hydride Reduction
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Acylation-rearrangement of N-tert-butyl and N-cyclohexyl nitrones of cyclohexanecarboxaldehyde (1), n-butyraldehyde, isobutyraldehyde, 3-cyclohexenecarboxaldehyde, and α-methylpropionaldehyde gave α-pivaloyloxy imines, which underwent reduction with lithi
- Coates, Robert M.,Cummins, Clark H.
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p. 1383 - 1389
(2007/10/02)
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- AN ALTERNATIVE PROCEDURE FOR THE ALUMINUM-MEDIATED CONVERSION OF ESTERS TO AMIDES
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A convenient method has been developed for directly converting esters to amides using reagents derived from the reaction of trimethylaluminum with ammonium chloride, methylamine hydrochloride or dimethylamine hydrochloride.
- Levin, Jeremy I.,Turos, Edward,Weinreb, Steven M.
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p. 989 - 994
(2007/10/02)
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