- Carboxylic Acid Deoxyfluorination and One-Pot Amide Bond Formation Using Pentafluoropyridine (PFP)
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This work describes the application of pentafluoropyridine (PFP), a cheap commercially available reagent, in the deoxyfluorination of carboxylic acids to acyl fluorides. The acyl fluorides can be formed from a range of acids under mild conditions. We also demonstrate that PFP can be utilized in a one-pot amide bond formation via in situ generation of acyl fluorides. This one-pot deoxyfluorination amide bond-forming reaction gives ready access to amides in yields of ≤94%.
- Brittain, William D. G.,Cobb, Steven L.
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supporting information
p. 5793 - 5798
(2021/08/01)
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- Synthesis and characterization of Pd(II)–vitamin B6 complex supported on magnetic nanoparticle as an efficient and recyclable catalyst system for C–N cross coupling of amides in deep eutectic solvents
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Vitamin B6–Pd(II) immobilized onto magnetic nanoparticles have been successfully prepared and applied for C–Xcross-coupling reactions with aryl halides in green deep eutectic solvents. The results prove that the Fe3O4@vitamin B6–Pd(II) magnetic nanoparticles show high catalyst activity and good stability. It was also revealed that this complex can be recycled up to five times without any significant loss in catalytic activity.
- Bagheri, Sepideh,Pazoki, Farzane,Esfandiary, Naghmeh,Fadaei, Mohammad Mahdi,Heydari, Akbar
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- Structure optimization of positive allosteric modulators of GABAB receptors led to the unexpected discovery of antagonists/potential negative allosteric modulators
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Positive allosteric modulators (PAMs) of GABAB receptor represent an interesting alternative to receptor agonists such as baclofen, as they act on the receptor in a more physiological way and thus are devoid of the side effects typically exerted by the agonists. Based on our interest in the identification of new GABAB receptor PAMs, we followed a merging approach to design new chemotypes starting from selected active compounds, such as GS39783, rac-BHFF, and BHF177, and we ended up with the synthesis of four different classes of compounds. The new compounds were tested alone or in the presence of 10 μM GABA using [35S]GTPγS binding assay to assess their functionality at the receptor. Unexpectedly, a number of them significantly inhibited GABA-stimulated GTPγS binding thus revealing a functional switch with respect to the prototype molecules. Further studies on selected compounds will clarify if they act as negative modulators of the receptor or, instead, as antagonists at the orthosteric binding site.
- Mugnaini, Claudia,Brizzi, Antonella,Mostallino, Rafaela,Castelli, Maria Paola,Corelli, Federico
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- Catalyst-Free Transamidation of Aromatic Amines with Formamide Derivatives and Tertiary Amides with Aliphatic Amines
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A simple catalyst- and promoter-free protocol has been developed for the transamidation of weakly nucleophilic aromatic amines with formamide derivatives and low-reactivity tertiary amides with aliphatic amines. This strategy is advantageous because no catalyst or promoters are needed, no additives are required, separation and purification is easy, and the reaction is scalable. Significantly, this strategy was further applied to synthesize several pharmaceutical molecules on a gram scale, and excellent yields were achieved.
- Yin, Jiawen,Zhang, Jingyu,Cai, Changqun,Deng, Guo-Jun,Gong, Hang
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supporting information
p. 387 - 392
(2019/01/11)
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- A non-catalyst non-promoter under the conditions of amide derivatives of aromatic amine with transfers the amine reaction
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The present invention discloses a non-catalyst under the condition of non-accelerator [...] amide derivatives of aromatic amine with transfers the amine reaction, yield of synthetic N - aryl amide derivatives. The method has a wide range of the substrate, its raw materials and cheap and easy to obtain acylation reagent, the reaction yield is high, one-step reaction, low cost, high reaction selectivity, simple operation and the like. Adopting this method can be gram scale can realize the high yield of the synthesis of drug molecules. Therefore, the method in the N - aryl amide derivatives of synthesis application field has very good application prospect. The method overcomes the existing technologies such as the reaction reagent toxicity is large, the need to use different type catalyst, synthesis method and the cost is high, more reaction steps, more byproducts and the like.
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Paragraph 0093; 0094
(2019/03/28)
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- Clickable coupling of carboxylic acids and amines at room temperature mediated by SO2F2: A significant breakthrough for the construction of amides and peptide linkages
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The construction of amide bonds and peptide linkages is one of the most fundamental transformations in all life processes and organic synthesis. The synthesis of structurally ubiquitous amide motifs is essential in the assembly of numerous important molecules such as peptides, proteins, alkaloids, pharmaceutical agents, polymers, ligands and agrochemicals. A method of SO2F2-mediated direct clickable coupling of carboxylic acids with amines was developed for the synthesis of a broad scope of amides in a simple, mild, highly efficient, robust and practical manner (>110 examples, >90% yields in most cases). The direct click reactions of acids and amines on a gram scale are also demonstrated using an extremely easy work-up and purification process of washing with 1 M aqueous HCl to provide the desired amides in greater than 99% purity and excellent yields.
- Wang, Shi-Meng,Zhao, Chuang,Zhang, Xu,Qin, Hua-Li
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p. 4087 - 4101
(2019/04/30)
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- Synthesis of benzamides through direct condensation of carboxylic acids and amines in the presence of diatomite earth@IL/ZrCl4 under ultrasonic irradiation
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A green, rapid, mild and highly efficient pathway for the preparation of benzamide derivatives is reported. The reaction was performed through direct condensation of benzoic acids and amines under ultrasonic irradiation in the presence of Lewis acidic ionic liquid immobilized on diatomite earth (diatomite earth@IL/ZrCl4). A new, highly efficient and green solid acid catalyst was easily prepared via a two-step procedure and used as an effective reusable catalyst. The prepared catalyst provides active sites for the synthesis of benzamides. The advantages of this method are the use of a superior and recoverable catalyst, low reaction times, simple procedure, high-yielding and eco-friendly process and use of ultrasonic irradiation as a green and powerful technology. Since benzamides are used widely in the pharmaceutical, paper and plastic industries, and also as an intermediate product in the synthesis of therapeutic agents, the presented new synthetic methods for this type of compounds can be of considerable importance.
- Ahmadi, Masoumeh,Moradi, Leila,Sadeghzadeh, Masoud
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p. 7873 - 7889
(2018/09/27)
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- BIARYLTRIAZOLE INHIBITORS OF MACROPHAGE MIGRATION INHIBITORY FACTOR
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The present disclosure describes biaryl triazole compounds, as well as their compositions and methods of use. The compounds inhibit the activity of macrophage migration inhibitory factor and are useful for the treatment of diseases, e.g., inflammatory dis
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Page/Page column 155
(2016/09/22)
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- AIBN-promoted amidation of anilines with 1, 3-diketones via oxidative cleavage of C–C bond under aerobic conditions
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N-Acylation of anilines with 1, 3-diketones promoted by AIBN (2-2′-azoisobutyronitrile) under metal-free and peroxide-free conditions in the presence of molecular oxygen as oxidant has been described. This protocol proceeds by the oxidative cleavage of C–C bond with simultaneous intermolecular C–N bond formation under mild conditions.
- Rao, Sadu Nageswara,Mohan, Darapaneni Chandra,Adimurthy, Subbarayappa
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p. 4889 - 4894
(2016/07/18)
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- Carboxyl activation of 2-mercapto-4,6-dimethylpyrimidine through n-acyl-4,6-dimethylpyrimidine-2-thione: A chemical and spectrophotometric investigation
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2-Mercapto-4,6-dimethylpyrimidine, as effective carboxyl activating group, has been successfully proved by converting it into respective acyl derivatives and the subsequent conversion to the amides and esters respectively using amines, amino alcohols and alcohols. The aminolysis and esterification were monitored chemically and spectrophotometrically. This paved way to establish that the above mercaptopyrimidine derivative is an efficient carboxyl activating group applicable in solid phase peptide synthesis.
- Rajan
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p. 287 - 291
(2015/01/30)
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- Design, synthesis, and protein crystallography of biaryltriazoles as potent tautomerase inhibitors of macrophage migration inhibitory factor
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Optimization is reported for biaryltriazoles as inhibitors of the tautomerase activity of human macrophage migration inhibitory factor (MIF), a proinflammatory cytokine associated with numerous inflammatory diseases and cancer. A combined approach was taken featuring organic synthesis, enzymatic assaying, crystallography, and modeling including free-energy perturbation (FEP) calculations. X-ray crystal structures for 3a and 3b bound to MIF are reported and provided a basis for the modeling efforts. The accommodation of the inhibitors in the binding site is striking with multiple hydrogen bonds and aryl-aryl interactions. Additional modeling encouraged pursuit of 5-phenoxyquinolinyl analogues, which led to the very potent compound 3s. Activity was further enhanced by addition of a fluorine atom adjacent to the phenolic hydroxyl group as in 3w, 3z, 3aa, and 3bb to strengthen a key hydrogen bond. It is also shown that physical properties of the compounds can be modulated by variation of solvent-exposed substituents. Several of the compounds are likely the most potent known MIF tautomerase inhibitors; the most active ones are more than 1000-fold more active than the well-studied (R)-ISO-1 and more than 200-fold more active than the chromen-4-one Orita-13.
- Dziedzic, Pawel,Cisneros, José A.,Robertson, Michael J.,Hare, Alissa A.,Danford, Nadia E.,Baxter, Richard H. G.,Jorgensen, William L.
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supporting information
p. 2996 - 3003
(2015/03/18)
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- H2O2-mediated oxidative formation of amides from aromatic amines and 1,3-diketones as acylation agents via C-C bond cleavage at room temperature in water under metal-free conditions
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1,3-Diketones, as novel acylation agents, reacted with aromatic amines promoted by commercially available H2O2 (30% aq.) as the sole oxidant at room temperature under metal-free conditions in water, leading to a novel and rapid amide bond formation strategy. The reported method is high-yielding, simple and mild, and is the first example of the use of 1,3-diketones as acylation agents via C-C bond cleavage.
- Sun, Xi,Wang, Min,Li, Pinhua,Zhang, Xiuli,Wang, Lei
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supporting information
p. 3289 - 3294
(2013/12/04)
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- Synthesis, X-ray crystallography, and reactions of N-acyl and N-carbamoyl succinimides
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A collection of N-acyl and N-carbamoyl succinimides were prepared by acylation of succinimide with acyl chlorides or by ethylene dichloride (EDC) coupling of carboxylic acids. The x-ray crystal structures of N-benzoyl and N-p-nitrobenzoyl succinimides were determined. The N-acyl succinimides were effective in acylating primary amines, a secondary amine, and an aromatic amine. Copyright
- Goodman, Cassie A.,Eagles, Joel B.,Rudahindwa, Leandre,Hamaker, Christopher G.,Hitchcock, Shawn R.
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supporting information
p. 2155 - 2164
(2013/07/25)
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- Isolation of magnetic material from fly ash and its catalytic performance for N-acetylation under solvent free conditions
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Coal fly ash is a waste material generated in huge amount due to'burning of coal for the generation of electricity. Magnetic material isolated from fly ash was characterized by XRD, FT-IR, SEM-EDS, XPS, BET and TEM techniques. It is used as heterogeneous catalyst for the JV-acetylation reactions of amines with carboxylic acids. The present methodology is environmentally benign, cost effective and offers several advantages, like excellent yields, short reaction times, reusability of catalyst and simple work up procedure. The case studies cover new approaches and experiments, which will articulate the requirement for industrial application of sustainable chemistry.
- Dhokte, Aashish O.,Shaikh, Uzmaparveen K.,Lande, Machhindra K.,Arbad, Babasaheb R.
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p. 837 - 844
(2013/08/23)
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- Direct hydrogenation of nitroaromatics and one-pot amidation with carboxylic acids over platinum nanowires
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A novel ultrathin platinum nanowire with uniform length and a diameter of 1.5 nm was synthesized by acidic etching of FePt nanowire in methanol. This nanowire was characterized by high-resolution transmission electron microscopy (HRTEM). X-ray diffraction (XRD) data indicated that the main plane is (111). The ability of this nanowire to catalyze the heterogeneous hydrogenation of nitroaromatics to give the corresponding amines has been investigated. The catalyst showed satisfactory activity in various solvents under mild conditions and showed excellent stability. The catalytic performance was also evaluated in the one-pot reduction of nitroaromatics and amidation with carboxylic acids under a hydrogen atmosphere at 100°C. These methods for the hydrogenation of nitroaromatics and the direct amidation of nitroaromatics with carboxylic acids are simple, economical, and environmentally benign, and have practical advantages for the synthesis of amines and amides without the production of toxic byproducts.
- Li, Min,Hu, Lei,Cao, Xueqin,Hong, Haiyan,Lu, Jianmei,Gu, Hongwei
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supporting information; experimental part
p. 2763 - 2768
(2011/04/12)
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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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- Hydrogen processing by FeIII-exchanged montmorillonite: A unique geochemical protocol
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The production of hydrogen by the relay of electrons from 1- to H+ in an acidic, aqueous medium and the consumption of hydrogen by reductive N acylation open up enormous opportunities in hydrogen chemistry (see scheme).
- Choudary, Boyapati M.,Kantam, Mannepalli L.,Ranganath, Kalluri V. S.,Rao, Kottapalli K.
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p. 322 - 325
(2007/10/03)
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- Method of processing of hydrogen for reductive acylation of nitro, azido and cyano arenes
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A method for processing of hydrogen for the reductive acylation of nitro, azido and cyano arenes is disclosed. More particularly, improved process for the preparation of amides and anilides using C3-C7carboxylic acids as proton source/acylating agents employing Fe3+-montmorillonite as a catalyst is disclosed.
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Page column 5
(2008/06/13)
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- Thermal behaviors of ionic liquids under microwave irradiation and their application on microwave-assisted catalytic Beckmann rearrangement of ketoximes
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Microwave-assisted Beckmann rearrangements of ketoximes in room temperature ionic liquids have been accomplished successfully using only 5 mol% of H2SO4 as a catalyst.
- Lee, Jae Kyun,Kim, Dok-Chan,Song, Choong Eui,Lee, Sang-Gi
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p. 2301 - 2307
(2007/10/03)
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- Rhodium-catalyzed Beckmann rearrangement
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equation presented Beckmann rearrangement of oxime is catalyzed by [RhCl(cod)]2, trifluoromethanesulfonic acid, and tris(p-tolyl)phosphine in refluxing dichloroethane, giving the corresponding amide in good yield. Product/acid ratios of 10:20 can be attained in the reaction of benzophenone oximes.
- Arisawa, Mieko,Yamaguchi, Masahiko
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p. 311 - 312
(2007/10/03)
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- Efficient synthesis of aromatic sec-amides from esters: Synthetic utility of bislithium amides
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Convenient, efficient preparation of aromatic sec-amides from esters has been accomplished using dilithium amides which are easily prepared by treatment of aromatic amines with 2 equiv of BuLi in THF. This new method allows a facile formation of amide bond even with sterically hindered esters.
- Ooi, Takashi,Tayama, Eiji,Yamada, Masao,Maruoka, Keiji
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p. 729 - 730
(2007/10/03)
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- Aminolysis of N-Acylpyrazoles
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1-Acylpyrazoles reacted with amines having a tiny substituted to afford the corresponding amides.The aminolysis with bulky amines was controlled to be retarded by the steric factors.Due to this steric interaction, the stereoselective aminolysis was observed.This selectivity of aminolysis should increase the utility of pyrazoles as auxiliary compounds in the synthetic loop.
- Kashima, Choji,Fukuchi, Iwao,Takahashi, Katsumi,Hosomi, Akira
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p. 1407 - 1412
(2007/10/02)
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