- Ethyl 2-Cyano-2-(2-nitrobenzenesulfonyloxyimino) Acetate (ortho-NosylOXY)-Mediated Double Beckmann Rearrangement of Ketoximes under Microwave Irradiation: A Mechanistic Perception
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A method for Beckmann rearrangement using ethyl 2-cyano-2-(2-nitrobenzenesulfonyloxyimino) acetate (o-NosylOXY) under microwave irradiation is reported. Ketoximes (19 examples) are converted to the corresponding amides/lactams with 69–97% yields in ～10 minutes without any Lewis acid or co-catalyst. This is an example of halogen-free organocatalytic Beckmann rearrangement. Nuclear magnetic resonance (NMR)- and high-resolution mass spectrometry (HRMS)-based detailed mechanistic investigation suggest that o-NosylOXY acts as an initiator. Such initiators are reported before based on density functional theory (DFT) calculations. However, we report here the HRMS signatures of two transient intermediates, the nitrilium ion and the nitrilium ion's dimeric species. Rigorous NMR-based investigation of the reaction mechanism is performed. Our results indicate that the reported Beckmann rearrangement proceeds via two consecutive rearrangements. (Figure presented.).
- Dev, Dharm,Kalita, Tapasi,Mondal, Tanmay,Mandal, Bhubaneswar
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p. 1427 - 1435
(2021/01/04)
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- Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles
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The Schmidt reaction has been an efficient and widely used synthetic approach to amides and nitriles since its discovery in 1923. However, its application often entails the use of volatile, potentially explosive, and highly toxic azide reagents. Here, we report a sequence whereby triflic anhydride and formic and acetic acids activate the bulk chemical nitromethane to serve as a nitrogen donor in place of azides in Schmidt-like reactions. This protocol further expands the substrate scope to alkynes and simple alkyl benzenes for the preparation of amides and nitriles.
- Jiao, Ning,Liu, Jianzhong,Qiu, Xu,Song, Song,Wei, Jialiang,Wen, Xiaojin,Zhang, Cheng,Zhang, Ziyao
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supporting information
p. 281 - 285
(2020/01/28)
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- Synthesis method 7- aminoheptanoic acid hydrochloride
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The invention discloses a synthesis method 7 - of, aminoheptanoic acid hydrochloride, belongs to the field: organic synthesis, and the reaction solution obtained by adding the cycloheptanone to the methanol solution, and adding concentrated HCl, to obtain, aminopimelic acid hydrochloride, is more suitable for large-scale production, by adding concentrated hydrochloric acid, reflux reaction 7 - to dichloromethane cooling crystallization. for producing the heptane lactam, in simple operation, of the present invention.
- -
-
Paragraph 0033-0042
(2020/03/16)
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- A novel synthetic route of fused tricyclic framework quinoline derivatives from readily available aliphatic amino carboxylic acid substrates
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A novel and an efficient strategy of fused tricyclic quinoline heterocycle compounds from aliphatic amino carboxylic acid substrates was studied. The protocol here is proceed over main reaction processes including: cyclization, protection, amidine formation, further cyclization and finally coupling with boronic acid substrate through Suzuki reaction. These reactions afforded the corresponding products in high yields. Furthermore, all synthesized compounds were identified by spectral data.
- Mohammed, Shireen
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p. 611 - 617
(2019/06/07)
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- In Situ Conformational Fixation of the Amide Bond Enables General Access to Medium-Sized Lactams via Ring-Closing Metathesis
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In this work, a novel phenethylamine-derived protecting group is introduced, which is able to significantly enhance the Grubbs I-catalyzed formation of 9- to 12-membered lactams through charge-induced conformational fixation under acidic conditions. As the new approach is particularly valuable for 10- and 11-membered ring systems, for which no related precedence was available so far, the overall strategy now offers general access to medium-sized lactams via ring closing metathesis. Cleavage of the protecting group can be achieved through a mild sequence combining N-oxidation and Cope elimination or alternatively under standard hydrogenation conditions.
- Hegmann, Nina,Prusko, Lea,Diesendorf, Nina,Heinrich, Markus R.
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supporting information
p. 7825 - 7829
(2019/01/04)
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- Construction of tertiary chiral centers by Pd-catalyzed asymmetric allylic alkylation of prochiral enolate equivalents
-
Abstract The palladium-catalyzed decarboxylative allylic alkylation of enol carbonates derived from lactams and ketones is described. Employing these substrates with an electronically tuned Pd catalyst system trisubstituted chiral centers are produced. These stereocenters have been previously challenging to achieve using Pd complex/chiral P-N ligand systems.
- Kita, Yusuke,Numajiri, Yoshitaka,Okamoto, Noriko,Stoltz, Brian M.
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p. 6349 - 6353
(2015/08/18)
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- Establishment of an activated peroxide system for low-temperature cotton bleaching using N-[4-(triethylammoniomethyl)benzoyl]butyrolactam chloride
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Cotton bleaching is traditionally carried out in strongly alkaline solution of hydrogen peroxide (H2O2) at temperatures close to the boil. Such harsh processing conditions can result in extensive water and energy consumptions as well as severe chemical damage to textiles. In this study, an activated peroxide system was established for low-temperature cotton bleaching by incorporating a bleach activator, namely N-[4-(triethylammoniomethyl)benzoyl]butyrolactam chloride (TBBC) into an aqueous H2O2 solution. Experimental results showed that the TBBC-activated peroxide system exhibited the most effective bleaching performance in a pH range of 6-8 which could be approximated by adding sodium bicarbonate (NaHCO3). The TBBC/H2O2/NaHCO3 system led to rapid bleaching of cotton at a temperature as low as 50°C. In comparison with the hot alkaline peroxide bleaching system, the TBBC/H2O2/NaHCO3 system provided cotton fabric with an equivalent degree of whiteness, higher degree of polymerization, and slightly lower water absorbency. The new activated peroxide system may provide a more environmentally benign approach to cotton bleaching.
- Xu, Changhai,Hinks, David,Sun, Chang,Wei, Qufu
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- A mild, copper-catalysed amide deprotection strategy: Use of tert-butyl as a protecting group
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Mild methods for the deprotection of organic substrates are of fundamental importance in synthetic chemistry. A new room temperature method using a catalytic amount of Cu(OTf)2is reported. This allows use of the tert-butyl group as an amide protecting group. The methodology is also extended to Boc-deprotection.
- Evans, Vikki,Mahon, Mary F.,Webster, Ruth L.
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supporting information
p. 7593 - 7597
(2014/12/10)
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- HISTONE DEACETYLASE 6 SELECTIVE INHIBITORS FOR THE TREATMENT OF BONE DISEASE
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This invention relates to methods for treating bone disease associated with osteoclast activation using HDAC6 selective inhibitors, e.g., small molecule inhibitors such as reverse amide compounds.
- -
-
Page/Page column 71-72
(2013/03/26)
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- Nano-sulfated titania (TiO2/SO2-4) as a new solid acid catalyst for Friedel-Crafts acylation and Beckman rearrangement in solvent-free conditions
-
The present work describes a novel application of nano-sulfated titania (nano-ST) as a solid acid catalyst for Friedel-Crafts acylation and Beckmann rearrangement. A nano-ST catalyst has been synthesized and characterized using various techniques such as XRD, scanning electron morphology, transmission electron microscopy, FT-IR, measurement of the specific surface area by Brunauer-Emmett-Teller theory and thermal analysis. The influences of various reaction parameters such as reaction temperature, molar ratio of reactants, reaction time and solvent effects have been investigated. [image omitted].
- Hosseini-Sarvari, Mona,Safary, Ensieh
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experimental part
p. 463 - 473
(2012/06/16)
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- REVERSE AMIDE COMPOUNDS AS PROTEIN DEACETYLASE INHIBITORS AND METHODS OF USE THEREOF
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The present invention relates to novel "reverse amide" compounds comprising a zinc chelator group, and the use of such compounds in the inhibition of HDAC6 and in the treatment of various diseases, disorders or conditions related to HDAC6.
- -
-
Page/Page column 76-78
(2011/08/08)
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- PTERIDINONES AS INHIBITORS OF POLO - LIKE KINASE
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The present invention provides compounds having a structure according to Formula (I) or a salt or solvate thereof, wherein ring A, X, R1, R2, R3, R4, R5 and R6, are defined herein. The invention further provides pharmaceutical compositions including the compounds of the invention and methods of making and using the compounds and compositions of the invention, e.g., in the treatment and prevention of various disorders, such as Parkinson's disease.
- -
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- Azido-Schmidt reaction for the formation of amides, imides and lactams from ketones in the presence of FeCl3
-
Ketones undergo smooth rearrangement with TMSN3 in the presence of FeCl3 under extremely mild conditions to provide the corresponding amides, imides and lactams in good yields with high selectivity. This method is very useful for the preparation of a wide range of amides, imides and lactams from ketones. The use of FeCl3 makes this method simple, convenient and cost-effective.
- Yadav,Reddy, B.V. Subba,Reddy, U.V. Subba,Praneeth
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p. 4742 - 4745
(2008/12/21)
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- An efficient and versatile one-pot Beckmann rearrangement of ketoximes using mesitylenesulfonyl chloride
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A variety of oxime mesitylenesulfonates, generated in situ from their heterocyclic, carbocyclic, and acyclic ketoximes in the presence of lithium hydroxide in tetrahydrofuran, efficiently rearrange into their corresponding lactams and amides. The stereochemistry of diazepan-5-one lactams resulting from the rearrangement of heterocyclic ketoximes (piperidin-4-one oximes), has been deduced based on one- and two-dimensional NMR analyses. The seven-membered heterocyclic ring of the product lactams adopts chair conformations with equatorial configurations of all the alkyl and aryl substituents except one of the methyl groups at C-3 on a 3,3-disubstituted product, which possess an axial configuration. Georg Thieme Verlag Stuttgart.
- Ramalingan, Chennan,Park, Yong-Tae
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p. 1351 - 1358
(2008/12/21)
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- Efficient tandem process for the catalytic deprotection of N-allyl amides and lactams in aqueous media: A novel application of the bis(allyl)- ruthenium(IV) catalysts [Ru(η3:η2: η3-C12H18)Cl2] and [Ru(η3:η3-C10H16)-(μ-Cl) Cl}2]
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An operationally simple and highly efficient methodology for the removal of the allyl protecting group in amides and lactams has been developed by using the commercially available bis(allyl)-ruthenium(IV) catalysts [Ru(η3:η2:η3-C12H 18)Cl2] (C12H18 = dodeca-2,6,10-triene-1,12-diyl) and [(Ru(η3:η3- C10H16)(μ-Cl)Cl}2] (C10H 16 = 2,7-dimethylocta-2,6-diene-1,8-diyl). The tandem process, which takes place in aqueous media and proceeds in a one-pot manner, involves the initial isomerization of the C=C bond of the allyl unit and subsequent oxidative cleavage of the resulting enamide.
- Cadierno, Victorio,Gimeno, Jose,Nebra, Noel
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p. 6590 - 6594
(2008/03/13)
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- Mercury-catalyzed rearrangement of ketoximes into amides and lactams in acetonitrile
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(Chemical Equation Presented) An acetonitrile solution of mercury(II) chloride has been found to catalyze efficiently the conversion of a diverse range of ketoximes into their corresponding amides/lactams.
- Ramalingan, Chennan,Park, Yong-Tae
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p. 4536 - 4538
(2008/02/04)
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- Silica sulfuric acid as a reusable catalyst for the conversion of ketones into amides by a Schmidt reaction under solvent-free conditions
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Silica sulfuric acid is a highly efficient reagent for the conversion of a variety of ketones into the corresponding amides by a Schmidt reaction under solvent-free conditions. Cyclic, aliphatic and aromatic ketones with electron-donating or withdrawing substituents may be converted easily in excellent yield. The major advantages of this method are: operational simplicity, the ready availability of the reagent, selectivity, general applicability, mild reaction conditions, short reaction times and high yields. The recovered catalyst could be used in new attempts without any purification.
- Eshghi, Hossein,Hassankhani, Asadollah,Mosaddegh, Elaheh
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p. 218 - 219
(2007/10/03)
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- P2O5/SiO2-catalyzed one-pot synthesis of amides from ketones via schmidt reaction under microwave irradiation in dry media
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A facile and efficient method for the preparation of amides from ketones by the Schmidt reaction is described for the first time using P 2 O 5 /SiO 2 and sodium azide under solvent-free microwave irradiation. Advantages of this procedure are selectivity, good yields, a simple operation, short reaction time, and solvent-free conditions. Copyright Taylor & Francis Group, LLC.
- Eshghi, Hossein,Hassankhani, Asadollah
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p. 2211 - 2216
(2007/10/03)
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- Alumina sulfuric acid mediated solvent-free and one-step Beckmann rearrangement of ketones and aldehydes and a useful reagent for synthesis of keto- and ald-oximes
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Under solvent-free conditions, one-step Beckmann rearrangement of a variety of ketones and aldehydes could proceed in the presence of alumina sulfuric acid (ASA). The ASA reagent can also be used for the preparation of keto- and ald-oximes.
- Hosseini-Sarvari, Mona,Sharghi, Hashem
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p. 205 - 208
(2007/10/03)
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- A convenient synthesis of medium-sized lactams through RCM reaction of oxyoxazolidinones
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Oxyoxazolidinones, which are prepared from secondary O-acylmandelamides by treatment with TBSOTf, underwent the RCM reaction in the presence of Grubbs catalyst to give oxazoloazepines or oxazoloazecines, which were readily converted into N-unsubstituted seven-membered or eight-membered lactams by the reductive treatment.
- Kamimura, Akio,Tanaka, Keiichi,Hayashi, Takahiro,Omata, Yoji
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p. 3625 - 3627
(2007/10/03)
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- Intramolecular Staudinger ligation: A powerful ring-closure method to form medium-sized lactams
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Efficient access to medium-sized lactams from co-amino acids that are resistant to ring-closure by traditional strategies is enabled by an intramolecular Staudinger ligation approach. An undesired premature Staudinger reaction is avoided by protecting the phosphane-containing auxiliary as a borane complex (see scheme; dabco = 1,4-diazabicyclo[2.2.2]octane).
- David, Olivier,Meester, Wim J. N.,Bieraeugel, Hans,Schoemaker, Hans E.,Hiemstra, Henk,Van Maarseveen, Jan H.
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p. 4373 - 4375
(2007/10/03)
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- Solvent-free and one-step Beckmann rearrangement of ketones and aldehydes by zinc oxide
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In the presence of zinc oxide and without any additional organic solvents, Beckmann rearrangement of several ketones and aldehydes were performed in good yields.
- Sharghi, Hashem,Hosseini, Mona
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p. 1057 - 1060
(2007/10/03)
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- One-step Beckmann rearrangement from carbonyl compounds and hydroxylamine hydrochloride in Al2O3/CH3SO3H (AMA) as a new reagent
-
A facile and efficient synthetic procedure, for one-step Beckmann rearrangement of aldehydes and ketones with hydroxylamine hydrochloride and Al2O3/CH3SO3H (AMA) has been developed; cyclohexanone has been converted into ε-caprolactam in a quantitative yield.
- Sharghi,Sarvari
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p. 446 - 449
(2007/10/03)
-
- Selective heterocyclic amidine inhibitors of human inducible nitric oxide synthase
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The potency and selectivity of a series of 5-hetero-2-iminohexahydroazepines were examined as inhibitors of the three human NOS isoforms. The effect of ring substitution of the 5-carbon for a heteroatom is presented. Potencies (IC50's) for these inhibitors are in the low micromolar range for hi-NOS with some examples exhibiting a 500× selectivity versus hec-NOS.
- Moormann, Alan E.,Metz, Sue,Toth, Mihaly V.,Moore, William M.,Jerome, Gina,Kornmeier, Christine,Manning, Pamela,Hansen Jr., Donald W.,Pitzele, Barnett S.,Webber
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p. 2651 - 2653
(2007/10/03)
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- Fast Synthesis of Amino Acid Salts and Lactams without Solvent under Microwave Irradiation
-
Hydroxylamine-O-sulfonic acid reacts with alicyclic ketones over SiO2 under microwave irradiation to give an amino acid salt, which cyclises in high yield to the corresponding lactam after work up in basic medium.
- Laurent, Alain,Jacquault, Patrick,Martino, Jean-Louis Di,Hamelin, Jack
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p. 1101 - 1102
(2007/10/02)
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- Triethylgallium Mediated Lactamization of α,ω-Amino Carboxylic Acids
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The 5-, 6-, 7-, and 8-membered lactams are obtained from the corresponding α,ω-amino carboxylic acids in good to high yields by treatment with triethylgallium in toluene or benzene.
- Yamamoto, Yoshinori,Furuta, Toshiaki
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p. 797 - 800
(2007/10/02)
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- Ruthenium Tetroxide Oxidation of N-Alkyllactams
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Ruthenium tetroxide (RuO4) oxidation of N-alkyllactams proceeded regioselectively depending on the size of lactam ring, except for the seven-membered ring.Four- and eight-membered N-methyl- and N-ethyllactams were oxidized at the exocyclic α-carbon adjacent to nitrogen to produce the N-acyllactams and NH-lactams, while five- and six-membered lactams underwent endocyclic oxidation to yield the cyclic imides.Oxidation of seven-membered lactams yielded a mixture of products arising from both exocyclic and endocyclic oxidations.These regioselectivities were confirmed in the oxidation of substrates having a tertiary carbon at the oxidation position.Keywords---oxidation; ruthenium tetroxide oxidation; regioselective oxidation; hydroxylation; imide synthesis; N-alkyllactam; N-acyllactams; imide; ruthenium tetroxide; two-phase method
- Yoshifuji, Shigeyuki,Arakawa, Yukimi,Nitta, Yoshihiro
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p. 357 - 363
(2007/10/02)
-
- Reactions of N- or N'-Blocked N-acylureas with Amines
-
In order to make reactions of N-acylureas with amines more selective N- or N'-blocked derivatives were prepared.Their fragmentation was examined.
- Schweim, Harald G.
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p. 430 - 437
(2007/10/02)
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- Tin-mediated esterification in macrolide synthesis
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A neutral and relatively simple new method for effecting internal macrocyclic esterification of omega -hydroxycarboxylic acids, based on a tin 'template-driven' extrusion process, is discussed and its application to the synthesis (macrocyclization step) of the macrolide antibiotics zearalenone, ingramycin, and nodusmicin detailed. An efficient, formal total synthesis of pyrenophorin using this technique is also presented. Attempts to extend the methodology to include the macrocyclization of omega -bromo carboxylic acids or omega -mercapto carboxylic acids were unsuccessful. However, although beta - and omega -amino carboxylic acids preferentially gave way to polymer formation, 4-,5, and 6-amino carboxylic acids readily condensed to give the corresponding five-, six-, and seven-membered lactams in excellent yields. For example, in this way, the bridged lactam 1-azabicyclo- left bracket 3. 3. 1 right bracket nonan-2-one was prepared in 77% yield as compared to the previously reported yield of less than 2%.
- Steliou,Poupart
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p. 7130 - 7138
(2007/10/02)
-
