- Hydrogenation of Secondary Amides using Phosphane Oxide and Frustrated Lewis Pair Catalysis
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The metal-free catalytic hydrogenation of secondary carboxylic acid amides is developed. The reduction is realized by two new catalytic reactions. First, the amide is converted into the imidoyl chloride by triphosgene (CO(OCCl3)2) using novel phosphorus(V) catalysts. Second, the in situ generated imidoyl chlorides are hydrogenated in high yields by an FLP-catalyst. Mechanistic and quantum mechanical calculations support an autoinduced catalytic cycle for the hydrogenation with chloride acting as unusual Lewis base for FLP-mediated H2-activation.
- K?ring, Laura,Sitte, Nikolai A.,Bursch, Markus,Grimme, Stefan,Paradies, Jan
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supporting information
p. 14179 - 14183
(2021/09/03)
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- Tert -Butyl nitrite promoted transamidation of secondary amides under metal and catalyst free conditions
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A mild and efficient method is demonstrated for the transamidation of secondary amides with various amines including primary, secondary, cyclic and acyclic amines in the presence of tert-butyl nitrite. The reaction proceeds through the N-nitrosamide intermediate and provides the transamidation products in good to excellent yields at room temperature. Moreover, the developed methodology does not require any catalyst or additives.
- Sureshbabu, Popuri,Azeez, Sadaf,Chaudhary, Priyanka,Kandasamy, Jeyakumar
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p. 845 - 850
(2019/01/30)
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- Chemoselective Synthesis of α-Amino-α-cyanophosphonates by Reductive Gem-Cyanation-Phosphonylation of Secondary Amides
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A novel approach to α-amino-α-cyanophosphonates has been developed. The method features a Tf2O-mediated reductive geminal cyanation/phosphonylation of secondary amides. Mild reaction conditions, high bond-forming efficiency, inexpensive readily available starting materials, and good to excellent yields with wide functional group compatibility constitute the main advantages of this method. The protocol can be run on a gram scale.
- Chen, Ting-Ting,Wang, Ai-E,Huang, Pei-Qiang
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supporting information
p. 3808 - 3812
(2019/05/24)
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- Tf2O-Mediated Intermolecular Coupling of Secondary Amides with Enamines or Ketones: A Versatile and Direct Access to β-Enaminones
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Based on the Tf2O-mediated intermolecular reaction of secondary amides with enamines derived from ketones, a novel approach to β-enaminones has been developed. The reaction is widely functional group tolerant and highly chemoselective. In the presence of 4 ? molecular sieves, the method can be extended to the one-pot condensation of secondary amides with ketones for NH β-enaminones synthesis.
- Liu, Yong-Peng,Zhu, Cheng-Jie,Yu, Cun-Cun,Wang, Ai-E,Huang, Pei-Qiang
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supporting information
p. 7169 - 7174
(2019/11/16)
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- The copper-catalyzed cross-coupling reactions of aryl diazonium salts and isocyanides
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The copper-catalyzed cross-coupling reaction of aryl diazonium salts and isocyanides has been performed. This is a successful example of preparation of arylcarboxyamides with moderate to good yield under mild conditions.
- Li,Cao,Zhu,Zhang,Shi
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p. 668 - 671
(2016/06/01)
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- TfOH catalyzed One-Pot Schmidt–Ritter reaction for the synthesis of amides through N-acylimides
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A One-Pot tandem Schmidt–Ritter process for the synthesis of amides has been developed using the super acid as catalyst. The in situ generated aryl/aliphatic nitriles from the reaction of aldehydes and sodium azide in the presence of TfOH and AcOH (Schmidt reaction) react with suitable alcohol (Ritter reaction) to give the amides. For the first time we observed that during the Schmidt process N-acylimides were generated along with nitriles, interestingly these N-acylimides also participated in the Ritter reaction.
- Singh, Garima,Dada, Ravikrishna,Yaragorla, Srinivasarao
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supporting information
p. 4424 - 4427
(2016/09/13)
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- Acid mediated deprotection of N-isopropyl tertiary amides
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Tertiary amides containing an N-isopropyl group were selectively deprotected by heating in methanesulfonic acid. The N-isopropyl group was removed selectively in the presence of other groups on the amide nitrogen such as methyl, primary alkyl, or aryl. The putative isopropyl cation was trapped by Friedel-Crafts alkylation of anisole when the latter was included as a co-solvent.
- Lorenc, Chris,Reeves, Jonathan T.,Busacca, Carl A.,Senanayake, Chris H.
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p. 1280 - 1282
(2015/03/04)
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- A transition-metal-free synthesis of arylcarboxyamides from aryl diazonium salts and isocyanides
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A transition-metal-free carboxyamidation process, using aryl diazonium tetrafluoroborates and isocyanides under mild conditions, has been developed. This novel conversion was initiated by a base and solvent induced aryl radical, followed by radical addition to isocyanide and single electron transfer (SET) oxidation, affording the corresponding arylcarboxyamide upon hydration of the nitrilium intermediate.
- Xia, Zhonghua,Zhu, Qiang
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p. 4110 - 4113
(2013/09/12)
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- Isoquinoline-catalyzed reaction of phenacyl bromide and N, N -dialkylcarbodiimides: Novel synthesis of azirines
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A practical and efficient procedure for the synthesis of polysubstituted azirines and in some cases benzamides was developed through reaction of phenacyl bromides and N,N-dialkylcarbodiimides, in the presence of catalytic amount of isoquinoline in dry ace
- Alizadeh, Abdolali,Rezvanian, Atieh
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experimental part
p. 859 - 862
(2012/05/20)
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- High-load, oligomeric monoamine hydrochloride: facile generation via ROM polymerization and application as an electrophile scavenger
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A new high-load, oligomeric monoamine hydrochloride (OMAm·HCl) derived from ring-opening metathesis polymerization (ROMP) of norbornene methylamine is reported. This oligomeric amine has been shown to be an effective scavenger of acid chlorides, sulfonyl chlorides, and isocyanates. The reagent can be synthesized in a straightforward protocol from the Diels-Alder reaction of dicyclopentadiene (DCPD) 1 with allylamine (neat), formation of the corresponding ammonium salt and subsequent ROM polymerization to afford the desired oligomeric ammonium salts.
- Stoianova, Diana S.,Yao, Lei,Rolfe, Alan,Samarakoon, Thiwanka,Hanson, Paul R.
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p. 4553 - 4555
(2008/09/21)
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- Lawesson's reagent for direct thionation of hydroxamic acids: Substituent effects on LR reactivity
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To explore the generality and scope of direct thionation of hydroxamic acids (HAs), the reaction of various structurally diverse HAs with Lawesson's reagent was investigated. The yield of thiohydroxamic acid (THAs) is poor when HAs possess bulky acyl and/or N-substituents, acidic α-hydrogen atoms, or an N-phenyl ring. THAs yields were correlated with Brown sigma parameter. The relative rates of two subsequent processes kT2 and kR2 were also measured. Correlation was also found for methine proton chemical shifts of N-isopropyl benzothiohydroxamic acids.
- Przychodzen, Witold
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p. 676 - 684
(2007/10/03)
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- Aryl triflates and [11C]/(13C)carbon monoxide in the synthesis of 11C-/13C-amides
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Palladium(0)-mediated carbonylation reactions using aryl triflates, amines, and a low concentration of [11C]carbon monoxide were used in the syntheses of 13 11C-labeled amides. Lithium bromide was used as an additive to facilitate the reaction. The 11C-labeled products were obtained with decay-corrected radiochemical yields in the range of 2-63%. The radiochemical purity of the final products exceeded 98%. As an example, a reaction starting with 1.79 GBq [11C]carbon monoxide gave 0.38 GBq of LC-purified N-isopropyl-4-nitro-[11C]benzamide within 27 min from the start of the carbonylation reaction (54% decay-corrected radiochemical yield). The specific radioactivity of this compound was 191 GBq/μmol, 35 min after the end of a 10 μAh bombardment. N-Benzyliso-quinoline-1-(13C)carboxamide was prepared and analyzed by NMR for confirmation of the labeling position. The triflates 16, 20, 21, and 22 were synthesized from the corresponding alcohols and trifluoromethanesulfonic anhydride. The reference compounds 30a and 30b were prepared from the corresponding carboxylic acids and benzylamine. The other nine reference compounds 32a to 32i were synthesized from the respective acid chlorides and amines. The presented report shows that the sometimes more easily obtainable aryl triflates can be a useful alternative to the commonly used aryl halides in palladium(0)-mediated synthesis of 11C/13C-amides.
- Rahman, Obaidur,Kihlberg, Tor,Langstroem, Bengt
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p. 3558 - 3562
(2007/10/03)
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- Substituted indolinones
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The present invention relates to indolinones substituted in the 6-position of general formula wherein R1 to R5 and X are defined as in claim 1, the isomers and the salts thereof, particularly the physiologically acceptable salts thereof which have valuable pharmacological properties, in particular an inhibiting effect on various receptor tyrosine kinases and cyclin/CDK complexes and on the proliferation of endothelial cells and various, pharmaceutical compositions containing these compounds, their use and processes for preparing them.
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- Kinetic stability of novel nitrile ylides
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A series of relatively stable novel trifluoromethyl substituted nitrile ylides have been generated by base promoted elimination of hydrogen chloride from the corresponding imidoyl chlorides in acetonitrile and aqueous dioxane solution at 25 °C. The format
- Hegarty, Anthony F.,Eustace, Stephen J.,Tynan, Nuala M.,Pham-Tran, Nguyen-Nguyen,Nguyen, Minh Tho
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p. 1239 - 1246
(2007/10/03)
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- Innovative synthesis of 4-carbaldehydepyrrolin-2-ones by zwitterionic rhodium catalyzed chemo- and regioselective tandem cyclohydrocarbonylation/CO insertion of α-imino alkynes
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The tandem cyclohydrocarbonylative/CO insertion of α-imino alkynes employs CO, H2, and catalytic quantities of zwitterionic rhodium complex (η6-C6H5 BPh3)-Rh+(1,5-COD) and triphenyl phosphite affording aldehyde substituted pyrrolinones in 67-82% yields. This unique transformation is readily applied to imino alkynes containing alkyl, alkoxyl, vinyl, and aryl substituents. The ability to prepare highly functionalized pyrrolinones makes this an attractive route to these important and versatile pharmaceuticals.
- Van den Hoven,Alper
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p. 10214 - 10220
(2007/10/03)
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- Benzamide therapeutics for the treatment of inflammatory bowel disease
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Benzamides are disclosed to be useful for treating and preventing inflammatory bowel disease.
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- Aminobenzamide compounds for the treatment of neurodegenerative disorders
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A group of benzamide compounds are disclosed which are useful for treating neurodegenerative disorders. Methods for making these compounds are provided. These materials are formed into pharmaceutical compositions for oral or intravenous administration to patients suffering from conditions such as Parkinson's disease which can exhibit themselves as progressive loss of central nervous system function. The compounds can arrest or slow the progressive loss of function.
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- S-triazine derivatives as light stabilizers
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S-triazine derivatives of formula (I): STR1 a process for the preparation thereof and the use thereof as light stabilisers.
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- S-triazine derivatives as light stabilisers
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S-triazine derivatives of formula (I): a process for the preparation thereof and the use thereof as light stabilisers.
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