- Practical Chemoselective Acylation: Organocatalytic Chemodivergent Esterification and Amidation of Amino Alcohols with N-Carbonylimidazoles
-
Chemoselective transformations are a cornerstone of efficient organic synthesis; however, achieving this goal for even simple transformations, such as acylation reactions, is often a challenge. We report that N-carbonylimidazoles enable catalytic chemodivergent aniline or alcohol acylation in the presence of pyridinium ions or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), respectively. Both acylation reactions display high and broad chemoselectivity for the target group. Unprecedented levels of chemoselectivity were observed in the DBU-catalyzed esterification: A single esterification product was obtained from a molecule containing primary aniline, alcohol, phenol, secondary amide, and N?H indole groups. These acylation reactions are highly practical as they involve only readily available, inexpensive, and relatively safe reagents; can be performed on a multigram scale; and can be used on carboxylic acids directly by in situ formation of the acylimidazole electrophile.
- Brown, Hailee,Heller, Stephen T.,Light, Christina,Medlin, Abigail,Nelson, Hope,Richard, William
-
supporting information
p. 22818 - 22825
(2021/09/13)
-
- Discovery of meta-amido bromophenols as new antitubercular agents
-
A series of meta-amido bromophenol derivatives were designed and synthesized. The compounds were found to potently inhibit the growth of Mycobacterium tuberculosis H37Ra. They also exhibited moderate inhibitory activity against Mycobacterium tuberculosis H37Rv and multidrug-resistant strains. The compounds did not show inhibitory activity against normal Gram-positive and Gram-negative bacteria. Moderate cytotoxicities and good metabolic stability were observed for the selected compounds. The results demonstrated meta-amido bromophenols as a new class of antitubercular agents with good potentials.
- Liang, Jie,Tang, Yun-xiang,Tang, Xiang-zheng,Liang, Hua-ju,Gao, Yamin,Fang, Cuiting,Zhang, Tian-yu,Yan, Ming
-
p. 372 - 381
(2019/05/07)
-
- Novel 3/4-((Substitutedbenzamidophenoxy)methyl)-N-hydroxybenzamides/propenamides and its use
-
The present invention relates to novel 3/4-((substituted benzamidophenoxy) methyl) -N-hydroxy benzamide/propenamide, as a histone deacetylase (HDAC) inhibitor, and to an anticancer composition comprising the same as an active ingredient. More specifically
- -
-
Paragraph 0101; 0103; 0104
(2020/03/17)
-
- Structure–activity relationship investigation of benzamide and picolinamide derivatives containing dimethylamine side chain as acetylcholinesterase inhibitors
-
A series of benzamide and picolinamide derivatives containing dimethylamine side chain (4a–4c and 7a–7i) were synthesised and evaluated for acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) inhibitory activity in vitro. Structure–activity relat
- Gao, Xiao-hui,Liu, Lin-bo,Liu, Hao-ran,Tang, Jing-jing,Kang, Lu,Wu, Hongnian,Cui, Peiwu,Yan, Jianye
-
p. 110 - 114
(2017/12/01)
-
- Amide type phytoalexin compound and preparation method thereof and whitening cosmetic composition containing it
-
The present invention relates to a phytoalexin compound having an amide structure represented by chemical formula 1, a production method thereof, and a whitening cosmetic composition containing the same. In the chemical formula 1, R_1 and R_2 are hydrogen, R_1 is hydroxy, and R_2 is hydrogen, or R_1 and R_2 are hydroxy.COPYRIGHT KIPO 2019
- -
-
Paragraph 0071-0074
(2019/02/16)
-
- A Cross-Coupling Approach to Amide Bond Formation from Esters
-
A palladium-catalyzed cross-coupling between aryl esters and anilines is reported, enabling access to diverse amides. The reaction takes place via activation of the C-O bond by oxidative addition with a Pd-NHC complex, which enables the use of relatively non-nucleophilic anilines that otherwise require stoichiometric activation with strong bases in order to react. High yields of aromatic, aliphatic, and heterocyclic products are obtained. A range of activated esters are evaluated in the presence and absence of catalyst, demonstrating that the catalytic methodology substantially increases the types of electrophiles that can be utilized for amide bond formation in the absence of harsh bases.
- Ben Halima, Taoufik,Vandavasi, Jaya Kishore,Shkoor, Mohanad,Newman, Stephen G.
-
p. 2176 - 2180
(2017/08/09)
-
- Fragmentation of Protonated N-(3-Aminophenyl)Benzamide and Its Derivatives in Gas Phase
-
An ion of m/z 110.06036 (ion formula [C6H8NO]+; error: 0.32 mDa) was observed in the collision induced dissociation tandem mass spectrometry experiments of protonated N-(3-aminophenyl)benzamide, which is a rearrangement product ion purportedly through nitrogen-oxygen (N–O) exchange. The N–O exchange rearrangement was confirmed by the MS/MS spectrum of protonated N-(3-aminophenyl)-O18-benzamide, where the rearranged ion, [C6H8NO18]+ of m/z 112 was available because of the presence of O18. Theoretical calculations using Density Functional Theory (DFT) at B3LYP/6-31?g(d) level suggest that an ion-neutral complex containing a water molecule and a nitrilium ion was formed via a transition state (TS-1), followed by the water molecule migrating to the anilide ring, eventually leading to the formation of the rearranged ion of m/z 110. The rearrangement can be generalized to other protonated amide compounds with electron-donating groups at the meta position, such as, –OH, –CH3, –OCH3, –NH(CH3)2, –NH-Ph, and –NHCOCH3, all of which show the corresponding rearranged ions in MS/MS spectra. However, the protonated amide compounds containing electron-withdrawing groups, including –Cl, –Br, –CN, –NO2, and –CF3, at the meta position did not display this type of rearrangement during dissociation. Additionally, effects of various acyl groups on the rearrangement were investigated. It was found that the rearrangement can be enhanced by substitution on the ring of the benzoyl with electron-withdrawing groups. [Figure not available: see fulltext.]
- Zu, Chengli,Mukhopadhyay, Sukrit,Hanley, Patrick S.,Xia, Shijing,Bell, Bruce M.,Grigg, David,Gilbert, Jeffrey R.,O’Brien, John P.
-
p. 917 - 926
(2016/05/02)
-
- 3-CARBOXY SUBSTITUTED COUMARIN DERIVATIVES WITH A POTENTIAL UTILITY FOR THE TREATMENT OF CANCER DISEASES
-
The present invention relates to novel compounds. The present invention also relates to the compounds for use as a medicine, more in particular for the prevention or treatment of cancer, more in particular cancers expressing MCT1 and/or MCT4. The present invention also relates to a method for the prevention or treatment of cancer in animals or humans by using the novel compounds. The present invention furthermore relates to pharmaceutical compositions or combination preparations of the novel compounds and to the compositions or preparations for use as a medicine, more preferably for the prevention or treatment of cancer. The present invention also relates to processes for the preparation of the compounds.
- -
-
Page/Page column 85
(2015/01/06)
-
- An improved protocol for synthesis of N-arylamides and benzoxazoles by the copper-catalyzed reaction of aryl halides with nitriles
-
An improved protocol for the synthesis of N-arylamides and benzoxazoles by the copper-catalyzed reaction of aryl halides with nitriles has been developed. Use of acetaldoxime as the hydrolysis reagent instead of H2O facilitates the operation of the reaction. The significantly decreased amount of nitriles, along with use of weak base K2CO3 instead of strong base KOH, makes this transformation atom-efficient and environmentally benign. A variety of N-arylamides and benzoxazole derivatives can be synthesized according to this approach.
- Zhang, Dong-Xue,Xiang, Shi-Kai,Hu, Hao,Tan, Wen,Feng, Chun,Wang, Bi-Qin,Zhao, Ke-Qing,Hu, Ping,Yang, Hua
-
p. 10022 - 10029
(2013/11/06)
-
- A library approach to the development of BenzaPhos: Highly efficient chiral supramolecular ligands for asymmetric hydrogenation
-
A library of chiral supramolecular ligands, named BenzaPhos, of straightforward preparation (two steps from commercially or readily available starting materials) and modular structure, was designed and synthesized. The ligands were screened in the search for new rhodium catalysts for the enantioselective hydrogenation of several benchmark and industrially relevant substrates. Once a series of hits were identified, structural modifications were introduced on three of the best ligands and a small second-generation library was created. Members of the latter library showed outstanding levels of activity and enantioselectivity in the hydrogenation of challenging olefins, such as enamide S4 and β-dehydroamino ester S5 (>99 % ee: best value ever reported in both cases). A series of control experiments were undertaken to clarify the role of hydrogen bonding in determining the catalytic properties of the new ligands. The results of these experiments, together with those of computational studies carried out on four dihydride complexes involved in the catalytic hydrogenation of substrate S4, strongly suggest that a substrate orientation takes place in the catalytic cycle by formation of a hydrogen bond between the ligand amide oxygen atom and the substrate amide NH atom. As simple as selective: BenzaPhos ligands, benzamide-containing chiral monophosphites of modular structure and trivial synthesis, have been screened in the Rh-catalyzed hydrogenation of olefins (see scheme), giving excellent enantioselectivities with three benchmark and two industrially relevant substrates. Control experiments and computational studies suggest an important role of ligand-substrate hydrogen bonding in the stereodiscriminating step of the catalytic cycle. Copyright
- Pignataro, Luca,Bovio, Chiara,Civera, Monica,Piarulli, Umberto,Gennari, Cesare
-
supporting information; experimental part
p. 10368 - 10381
(2012/10/08)
-
- Copper(II)-mediated cascade oxidative C-C coupling and aromatization: Synthesis of 3-hydroxyphenanthridinone derivatives
-
A novel copper(II) acetate mediated synthesis of 3-hydroxyphenanthridin- 6(5H)-ones from N-(3-oxocyclohex-1-enyl)benzamides was developed. The process is postulated to involve an intramolecular oxidative C(sp2)-C(sp 3) bond formation
- Yu, Qingzhen,Zhang, Nan,Tang, Yang,Lu, Hang,Huang, Jianhui,Wang, Songqing,Du, Yunfei,Zhao, Kang
-
supporting information; experimental part
p. 2374 - 2384
(2012/09/07)
-
- Copper-catalyzed synthesis of benzoxazoles via a regioselective C-H functionalization/C-O bond formation under an air atmosphere
-
(Chemical Equation Presented) An efficient method for the synthesis of functionalized benzoxazoles is described that involves a copper(II)-catalyzed regioselective C-H functionalization/C-O bond formation protocol. The use of dichlorobenzene as a solvent at 160°C allows the use of air as the terminal oxidant in the catalytic synthesis of benzoxazoles in a process that has high functional group tolerance. The presence of a directing group at the meta position markedly improves the reaction efficacy and a variety of 7-substituted benzoxazoles are selectively produced under mild reaction conditions. The mechanism of the reaction is also discussed in this report.
- Ueda, Satoshi,Nagasawa, Hideko
-
supporting information; experimental part
p. 4272 - 4277
(2009/09/08)
-
- Aminolysis of allyl esters with bislithium aryl amides
-
The aminolysis of allyl esters with bislithium amides is reported. Tertiary aryl amides were synthesized in a one-pot reaction with bislithium amides and a suitable electrophile in good yields. The scope of this reaction was demonstrated with a variety of anilines and aminopyridines and applied to the synthesis of triphenylmethylacetamides.
- Faler, Catherine A.,Joullié, Madeleine M.
-
p. 7229 - 7231
(2007/10/03)
-
- Three new derivatives of 3-amino-1,2-propanediol; their spectral properties and biological evaluation
-
Three new derivatives of 3-amino-1,2-propanediol have been synthesized. Full assignments of signals in their 1H- and 13C-NMR spectra are given. The influence of these compounds on the cardiovascular system in the anaesthetized rat was examined. In contrast to CGP 12177 which induced a strong increase in heart rate and a slight increase in blood pressure, compounds 1, 2 and 3 × HCI at doses up to 1 μmol/kg and compound 3 at doses of 0.01 and 0.1 μmol/kg did not change the cardiovascular parameters. The highest dose of compound 3 - 1 μmol/kg caused a very short-lasting decrease in heart rate (by 14%) and in blood pressure (by 25%).
- Morzycki,Maj,Nikitiuk,Kwolek,Malinowska
-
p. 249 - 256
(2007/10/03)
-
- HYDROXYLATION DIRECTE D'ESTERS DE PHENYLE ET D'ANILIDES PAR LE PEROXYDE D'HYDROGENE EN MILIEU SUPERACIDE
-
In SbF5-HF, hydrogen peroxide reacts on the aromatic ring of esters 1a-5a and anilides 11a-15a to give monohydroxylated derivatives in good yields.With compounds 2a, 4a and 5a, meta or para isomers are by far the major products, whereas with formate 1a and benzoate 3a, the proportion of the ortho isomer is more important.With anilides, the reaction is less selective, the three isomers being obtained in comparable amounts.Thus, the relative proportions of ortho, meta and para-hydroxylated derivatives obtained using 70 percent H2O2 with acetate 2a and acetanilide 12a are 6/51/43 and 36.5/30/33.5, respectively.The important proportion of meta hydroxylation is the result of the reaction of protonated hydrogen peroxide H3O2+ on the protonated substrate.
- Berrier, Christian,Jacquesy, Jean-Claude,Jouannetaud, Marie-Paule,Morellet, Guy
-
p. 158 - 164
(2007/10/02)
-
- Polymer-Bound Mixed Carboxylic Dithiocarbamic Anhydrides. A New Class of Selective and Recyclable Solid-Phase Acylating Reagents
-
Polymer-supported mixed carboxylic dithiocarbamic anhydrides are a new class of regenerable solid-phase reagents for acylating amino groups specifically.The resins were prepared by a four-step synthesis from cross-linked poly(chloromethylstyrene) (Merrifield's resin).The chloromethyl groups were converted to aminomethyl groups by the Gabriel synthesis, and reaction of the aminomethyl resin with carbon disulfide and aqueous sodium hydroxide gave a dithiocarbamate resin.Treatment of this resin with an acyl chloride gave the mixed carboxylic dithiocarbamic anhydride resin.These insoluble anhydrides transfer the acyl group to amines or amino acids in solution at room temperature, yielding a solution of the corresponding amide or peptide.The spent polymeric reagent can be regenerated to the carboxylic dithiocarbamic anhydride by treatment with carbon disulfide and sodium hydroxide followed by acylation.
- Haridasan, V. K.,Ajayaghosh, A.,Pillai, V. N. Rajasekharan
-
p. 2662 - 2665
(2007/10/02)
-
- DIANTHALEXINE, NOUVELLE PHYTOALEXINE, DE TYPE BENZOXAZINONE, ISOLEE DE L'OEILLET DIANTHUS CARYOPHYLLUS L. (CARYOPHYLLACEES).
-
The major phytoalexin from carnation has been identified as 7-hydroxy 2-phenyl 4H-3, 1-benzoxazin-4-one, and named dianthalexin (1).
- Bouillant, Marie-Louise,Favre-Bonvin, Jean,Ricci, Pierre
-
-
- KINETICS OF ACYLATION OF ANILINES MONOSUBSTITUTED IN THE RING BY BENZOYL CHLORIDE IN N,N-DIMETHYLACETAMIDE
-
The kinetics of the acylation of meta- and para-substituted primary arylamines by benzoyl chloride in N,N-dimethylacetamide was studied.The sensitivity of the reaction to changes in the structure of the arylamine in N,N-dimethylacetamide is lower than in other organic solvents.A mechanism involving catalysis of the acylation reaction by the solvent molecules is proposed.
- Kuz'min, N. I.,Kabanova, N. I.,Zhizdyuk, B. I.,Chegolya, A. S.
-
p. 2139 - 2141
(2007/10/02)
-