- Organophosphane-Promoted Synthesis of Functionalized α,β-Unsaturated Alkenes and Furanones via Direct β-Acylation
-
We report a phosphine-mediated direct β-acylation of α,β-unsaturated 1,3-diketones with acyl chlorides and a base. Functionalized furanones were also prepared by the reaction of cinnamic acid and acyl chloride according to our protocol via β-acylation. Our studies revealed that α,β-unsaturated 1,3-diketones with an electron-donating group at the second position favor the formation of β-acylated products, whereas those with oxygen, such as anhydrides, favor furanones via an unprecedented C-acylation/cyclization sequence.
- Liou, Yan-Cheng,Su, Yin-Hsiang,Ku, Kuan-Chun,Edukondalu, Athukuri,Lin, Chun-Kai,Ke, You-Syuan,Karanam, Praneeth,Lee, Chia-Jui,Lin, Wenwei
-
supporting information
p. 8339 - 8343
(2019/10/16)
-
- Symmetric imide compound and synthetic method thereof
-
The invention discloses a symmetric imide compound and a synthetic method thereof. The method comprises the steps of mixing a compound as shown in the general formula (I) and alkali in aprotic solvent, heating for reaction, and then collecting a compound as shown in the general formula (II) from the reaction product. A series of diaryl imide compounds with representative structure can be obtainedby one-step reaction of simple and easily available activated amide, which is taken as raw material.
- -
-
Paragraph 0030-0033
(2019/08/07)
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- Palladium-Catalyzed Solvent-Controlled Selective Synthesis of Acyl Isoureas and Imides from Amides, Isocyanides, Alcohols and Carboxylates
-
A highly selective synthesis of acyl isoureas and imides from readily accessible amides, isocyanides, alcohols and carboxylates based on reaction solvent selection is described. In the presence of a catalytic amount of [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) and cupric acetate, treatment of amides and isocyanides in alcohols at 60 °C provided acyl isoureas in high yields. Interestingly, when other solvents such as acetonitrile was used instead of alcohols, imides were exclusively produced in good to excellent yields via direct N-acylation of amides with carboxylates as the acyl sources. This protocol offers an attractive alternative approach toward isoureas and imides. (Figure presented.).
- Cao, Ming,Liu, Liqiu,Tang, Shi,Peng, Zhiyuan,Wang, Yingchun
-
p. 1887 - 1895
(2019/03/11)
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- Copper-Catalyzed Oxidative C?H Bond Functionalization of N-Allylbenzamide for Regioselective C?N and C?O Bond Formation
-
Copper-catalyzed oxidative couplings of N-allylbenzamides for C?N and C?O bond formations have been developed through C?H bond functionalization. To demonstrate the utility of this approach, it was applied to the synthesis of β-aminoimides and imides. To the best of our knowledge, these are the first examples in which different classes of N-containing compounds have been directly prepared from the readily available N-allylbenzamides using an inexpensive catalyst/oxidant/base (CuSO4/TBHP/Cs2CO3) system.
- Ranjith, Jala,Krishna, Palakodety Radha
-
supporting information
p. 1448 - 1451
(2019/04/03)
-
- CuCl/TMEDA/nor-AZADO-catalyzed aerobic oxidative acylation of amides with alcohols to produce imides
-
Although aerobic oxidative acylation of amides with alcohols would be a good complement to classical synthetic methods for imides (e.g., acylation of amides with activated forms of carboxylic acids), to date, there have been no reports on oxidative acylation to produce imides. In this study, we successfully developed, for the first time, an efficient method for the synthesis of imides through aerobic oxidative acylation of amides with alcohols by employing a CuCl/TMEDA/nor-AZADO catalyst system (TMEDA = teramethylethylendiamine; nor-AZADO = 9-azanoradamantane N-oxyl). The proposed acylation proceeds through the following sequential reactions: aerobic oxidation of alcohols to aldehydes, nucleophilic addition of amides to the aldehydes to form hemiamidal intermediates, and aerobic oxidation of the hemiamidal intermediates to give the corresponding imides. This catalytic system utilizes O2 as the terminal oxidant and produces water as the sole by-product. An important point for realizing this efficient acylation system is the utilization of a TMEDA ligand, which, to the best of our knowledge, has not been employed in previously reported Cu/ligand/N-oxyl systems. Based on experimental evidence, we consider that plausible roles of TMEDA involve the promotion of both hemiamidal oxidation and regeneration of an active CuII-OH species from a CuI species. Here promotion of hemiamidal oxidation is particularly important. Employing the proposed system, various types of structurally diverse imides could be synthesized from various combinations of alcohols and amides, and gram-scale acylation was also successful. In addition, the proposed system was further applicable to the synthesis of α-ketocarbonyl compounds (i.e., α-ketoimides, α-ketoamides, and α-ketoesters) from 1,2-diols and nucleophiles (i.e., amides, amines, and alcohols).
- Kataoka, Kengo,Wachi, Keiju,Jin, Xiongjie,Suzuki, Kosuke,Sasano, Yusuke,Iwabuchi, Yoshiharu,Hasegawa, Jun-Ya,Mizuno, Noritaka,Yamaguchi, Kazuya
-
p. 4756 - 4768
(2018/06/07)
-
- A carbonylation reaction of carbon monoxide in the method of preparing amide
-
The invention belongs to the technical field of synthesis of amides, discloses a process for the carbonylation of carbon monoxide in the method of preparing amide, the method is to cheap and easy to obtain the halogenated aromatic hydrocarbon and organic amine compounds as the substrate of reaction, to carbon monoxide as carbonyl source, under light-struck, halogenated aromatic hydrocarbons are cracked to produce free radical, by free-radical addition process to obtain the amide compound. Compared with the traditional carbonylation reaction, the carbon monoxide pressure is extremely low, can react to the atmospheric pressure. This process does not need to rely on any metal catalyst of the booster, mild reaction conditions, environmental protection, with a shorter synthetic route and high utilization efficiency of the atoms, the reaction system with higher substrate tolerance, green sustainable light source as the driving force, the atom economy is high, application prospect.
- -
-
Paragraph 0024; 0025; 0026; 0027; 0028-0032; 0129-0130; 0146
(2018/07/30)
-
- Vanadium-Catalyzed Oxidative C(CO)-C(CO) Bond Cleavage for C-N Bond Formation: One-Pot Domino Transformation of 1,2-Diketones and Amidines into Imides and Amides
-
A novel vanadium-catalyzed one-pot domino reaction of 1,2-diketones with amidines has been identified that enables their transformation into imides and amides. The reaction proceeds by dual acylation of amidines via oxidative C(CO)-C(CO) bond cleavage of 1,2-diketones to afford N,N′-diaroyl-N-arylbenzamidine intermediates. In the reaction, these intermediates are easily hydrolyzed into imides and amides through vanadium catalysis. This method provides a practical, simple, and mild synthetic approach to access a variety of imides as well as amides in high yields. Moreover, one-step construction of imide and amide bonds with a long-chain alkyl group is an attractive feature of this protocol.
- Digwal, Chander Singh,Yadav, Upasana,Ramya, P. V. Sri,Sana, Sravani,Swain, Baijayantimala,Kamal, Ahmed
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p. 7332 - 7345
(2017/07/26)
-
- Transition-Metal- and Halogen-Free Oxidation of Benzylic sp 3 C-H Bonds to Carbonyl Groups Using Potassium Persulfate
-
Aryl carbonyl compounds including acetophenones, benzophenones, imides, and benzoic acids are prepared from benzyl substrates using potassium persulfate as oxidant with catalytic pyridine in acetonitrile under mild conditions. Neither transition metals nor halogens are involved in the reactions.
- Hu, Yixin,Zhou, Lihong,Lu, Wenjun
-
p. 4007 - 4016
(2017/08/29)
-
- Organocatalytic Direct N-Acylation of Amides with Aldehydes under Oxidative Conditions
-
The direct oxidative N-acylation reaction of primary amides with aryl/α,β-unsaturated aldehydes was achieved in the presence of azolium salt C3 and an inorganic base using 3,3′,5,5′-tetra-tert-butyldiphenoquinone as the oxidant, thus providing an efficient approach for the synthesis of three types of imide compounds including N-sulfonylcarboxamides, N-sulfinylcarboxamides, and dicarboxyimides in good yield.
- Zheng, Chenguang,Liu, Xiang,Ma, Cheng
-
p. 6940 - 6945
(2017/07/13)
-
- Direct Oxidative Cross-Coupling of Toluene Derivatives and N-Acyl-2-aminoacetophenones
-
The direct oxidative cross-coupling between N-acyl-2-aminoacetophenones and toluene derivatives was developed with a new C–C bond being formed under metal-free and environmentally friendly conditions with excellent atom economy. A possible reaction pathway for the formation of the products is also discussed in this paper. (Figure presented.).
- Yu, Hui,Xu, Yilan,Dong, Rui,Fang, Yan
-
supporting information
p. 39 - 43
(2017/01/14)
-
- Synthesis and characterization of novel organic heteroatom compounds from reaction of Woollins' reagent with various organic substrates
-
A series of new selenium-containing heteroatom compounds were synthesized in good yields by the reaction of Woollins reagent with various organic substrates such as cyclohexylamine, N-benzoylbenzamide, benzoic anhydride, 4-fluoro-N-(2-oxo-2-phenylethyl)benzamide, N-benzoylbenzamide, benzoic anhydride, 3-(bromomethyl)benzonitrile, 1,2-diphenylethane-1,2-diol, and sodium alcoholate. Three representative X-ray structures are described.
- Hua, Guoxiong,Du, Junyi,Cordes, David B.,Arachchige, Kasun S. A.,Slawin, Alexandra M. Z.,Woollins, J. Derek
-
p. 341 - 346
(2016/04/05)
-
- Acidylation method of amine
-
The invention discloses an acidylation method of amine.The method includes the following steps that amine derivatives, hydrazide derivatives, organic peroxide and a catalyst are dissolved in a solvent and react at the temperature of 40-80 DEG C, and amide derivatives are obtained.The amide derivatives and hydrazide derivatives serve as initiators, the raw materials are easy to obtain and the number of varieties is large.Products obtained through the method are diverse in type, can be directly used and can also be used for other further reactions.The method is mild in reaction condition, simple in reaction operation and post-processing process, high in product yield and suitable for scale production.
- -
-
Paragraph 0035
(2016/10/10)
-
- Organic fluorine involved intramolecular hydrogen bonds in the derivatives of imides: NMR evidence corroborated by DFT based theoretical calculations
-
The rare occurrence of intramolecular hydrogen bonds (HBs) of the type N-H...F-C is detected in the derivatives of imides in a low polarity solvent by using multi-dimensional and multinuclear NMR experiments. The observation of 1hJFH, 2hJFN, and 2hJFF, where the spin magnetization is transmitted through space among the interacting NMR active nuclei, provided strong and unambiguous evidence for the existence of intra-molecular HBs. The variation in the chemical shifts of labile protons depending on physical conditions, such as the solvent dilution and the systematic alteration of temperature confirmed the presence of weak interactions through intramolecular HBs in all the investigated fluorine substituted molecules. The self or cross dimerization of molecules is unequivocally discarded by the analysis of the rates of diffusion obtained using pseudo-two dimensional DOSY experiments. The Density Function Theory (DFT) calculations based on the Quantum Theory of Atoms In Molecules (QTAIM) and Non Covalent Interaction (NCI), are in close agreement with the NMR experimental findings.
- Mishra, Sandeep Kumar,Suryaprakash
-
p. 86013 - 86022
(2015/11/03)
-
- Copper-catalyzed synthesis of imides from aldehydes or alcohols and amine hydrochloride salts
-
An efficient approach to imides has been developed. With tert-butyl hydroperoxide (TBHP) as the oxidant, CuBr (20 mol-%) as the catalyst, and PhI(OAc)2 (50 mol-%) as the additive, aldehydes or alcohols reacted with amine hydrochloride salts to provide imides in moderate to good yields. A possible reaction pathway for the formation of the products is also discussed in this paper.
- Yu, Hui,Zhang, Yonghao
-
p. 1824 - 1828
(2015/05/27)
-
- Formation of Amides from Imines via Cyanide-Mediated Metal-Free Aerobic Oxidation
-
A new protocol for the direct formation of amides from imines derived from aromatic aldehydes via metal-free aerobic oxidation in the presence of cyanide is described. This protocol was applicable to various aldimines, and the desired amides were obtained in moderate to good yields. Mechanistic studies suggested that this aerobic oxidative amidation might proceed via the addition of cyanide to imines followed by proton transfer from carbon to nitrogen in the original imines, leading to carbanions of α-amino nitriles, which undergo subsequent oxidation with molecular oxygen in air to provide the desired amide compounds.
- Seo, Hong-Ahn,Cho, Yeon-Ho,Lee, Ye-Sol,Cheon, Cheol-Hong
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p. 11993 - 11998
(2016/01/09)
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- TBHP/TEMPO-mediated oxidative synthesis of imides from amides
-
A new protocol for the synthesis of imides has been developed. In the presence of copper catalyst, N-benzylamides were oxidized to the corresponding imides by TBHP/TEMPO system in moderate to good yields. Imides were synthesized through the oxidation of N-benzylamides by TBHP/TEMPO system in moderate to good yields.
- Yu, Hui,Chen, Yuegang,Zhang, Yonghao
-
p. 531 - 534
(2015/05/27)
-
- Palladium-catalyzed aminocarbonylation of aryl iodides with amides and N-alkyl anilines
-
A novel and efficient palladium-catalyzed aminocarbonylation of aryl iodides with amides and N-alkyl anilines has been developed. The reaction tolerates a wide range of functional groups and is a reliable method for the rapid synthesis of a variety of valuable imides and tertiary benzanilides under an atmospheric pressure of CO. Copyright
- Ran, Longfei,Ren, Zhi-Hui,Wang, Yao-Yu,Guan, Zheng-Hui
-
p. 577 - 583
(2014/02/14)
-
- 2-Chloroanthraquinone-catalyzed aerobic photo-oxidative synthesis of diacylamines from benzylamides
-
In this Letter, we report the aerobic photo-oxidative synthesis of diacylamines from benzylamides in the presence of molecular oxygen and catalytic amounts of 2-chloroanthraquinones under visible light irradiation from a fluorescent lamp.
- Itoh, Izuho,Matsusaki, Yoko,Fujiya, Akitoshi,Tada, Norihiro,Miura, Tsuyoshi,Itoh, Akichika
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p. 3160 - 3162
(2014/05/20)
-
- Efficient synthesis of hydroxyl isoindolones by a Pd-mediated C-H activation/annulation reaction
-
Radical reaction: A convenient synthesis of hydroxyl isoindolones by a Pd-catalyzed C-H activation/annulation reaction with near "click chemistry" efficiency is presented (see scheme; TBHP=tert-butyl hydrogen peroxide). This methodology features short reaction times (10-30 min), high atom economy, wide substrate scope (22 examples), and good reaction yields (up to 93 %). Copyright
- Yu, Qingzhen,Zhang, Nana,Huang, Jianhui,Lu, Shaonan,Zhu, Yi,Yu, Xiaoxiao,Zhao, Kang
-
supporting information
p. 11184 - 11188
(2013/09/02)
-
- Exploration of an imide capture/N,N-acyl shift sequence for asparagine native peptide bond formation
-
Imide capture of a C-terminal peptidylazide with a side-chain thioacid derivative of an N-terminally protected aspartyl peptide leads to the formation of an imide bond bringing the two peptide ends into close proximity. Unmasking of the Nα protecting group and intramolecular acyl migration results in the formation of a native peptide bond to asparagine.
- Mhidia, Reda,Boll, Emmanuelle,Fécourt, Fabien,Ermolenko, Mikhail,Ollivier, Nathalie,Sasaki, Kaname,Crich, David,Delpech, Bernard,Melnyk, Oleg
-
p. 3479 - 3485
(2013/07/05)
-
- Synthesis of 1,3,5-trisubstituted-1,2,4-triazoles by microwave-assisted N-acylation of amide derivatives and the consecutive reaction with hydrazine hydrochlorides
-
Facile and efficient procedures for the N-acylation reaction of amide derivatives with various acid anhydrides and the cyclization reaction of N-acylated amide derivatives with various hydrazine hydrochlorides were described. The reactions were carried out under microwave irradiation to give products in good yields in a few minutes. The synthesis of 1,3,5-trisubstituted- 1,2,4-triazoles from benzamides can also be accomplished in a simple one-pot sequential reaction.
- Lee, Jongbok,Hong, Myengchan,Jung, Yoonchul,Cho, Eun Jin,Rhee, Hakjune
-
p. 2045 - 2051
(2012/04/10)
-
- Replacement of BF4- by PF6- makes Selectfluor greener
-
A combination of F-TEDA-PF6 and CuBr (0.1 equiv.) provides a potent oxidant that readily oxidizes amides to provide imides at room temperature. Replacement of BF4-, the anion of Selectfluor (F-TEDA-BF4), by PF6-, dramatically reduces CuBr loading in this oxidative reaction. A possible rationale for this dramatic counterion effect is provided.
- Jin, Zhuang,Xu, Bo,Hammond, Gerald B.,Dimagno, Stephen G.
-
p. 226 - 230,5
(2020/08/20)
-
- ZnO and ZnO-nanoparticles: Efficient and reusable heterogeneous catalysts for one-pot synthesis of N-acylsulfonamides and sulfonate esters
-
Commercially available and preparative ZnO nanoparticles are reported as efficient and reusable catalysts for the chemoselective synthesis of N-acylsulfonamides and sulfonate esters. A one-pot sequential sulfonylation and acylation of amines took place to afford the N-acylsulfonamides in excellent yields under solvent-free conditions. The ZnO catalyst can be reused for without significant loss of catalytic activity.
- Tamaddon, Fatemeh,Sabeti, Mohammad Reza,Jafari, Abbas Ali,Tirgir, Farhang,Keshavarz, Elham
-
body text
p. 41 - 45
(2012/01/12)
-
- Copper mediated oxidation of amides to imides by Selectfluor
-
The combination of Selectfluor and copper(I) bromide has shown a strong oxidation ability, readily oxidizing amides into the corresponding imides in acetonitrile at room temperature in less than 1 h. This transformation under mild conditions gives good to excellent chemical yields. A possible reaction mechanism is proposed.
- Jin, Zhuang,Xu, Bo,Hammond, Gerald B.
-
p. 1956 - 1959
(2011/04/25)
-
- Metal-free synthesis of imido derivatives by direct oxidation of α-amido sulfones
-
Oxidation of α-amidoaryl sulfones with m-chloroperoxybenzoic acid under mild conditions readily provides the corresponding imides in satisfactory yields. The overall processprobably involves formation of an N-acyliminium ion intermediate, which by attack
- Martinelli, Fabio,Palmieri, Alessandro,Petrini, Marino
-
experimental part
p. 5085 - 5089
(2010/10/21)
-
- Aerobic photooxidation of benzylamide under visible light irradiation with a combination of 48% aq HBr and Ca(OH)2
-
Benzylamides were found to be oxidized to their corresponding diacylamines in the presence of molecular oxygen, catalytic 48% aq HBr, and Ca(OH) 2 under visible light irradiation of a fluorescent lamp.
- Tada, Norihiro,Ban, Kazunori,Yoshida, Momoko,Hirashima, Shin-Ichi,Miura, Tsuyoshi,Itoh, Akichika
-
experimental part
p. 6098 - 6100
(2011/01/04)
-
- Accessing the amide functionality by the mild and low-cost oxidation of imine
-
Oxidation of imines using sodium chlorite under buffered conditions gave the corresponding amides in good to high yield. The reaction was generally fast and was completed within 5-40 min. As has been established in the corresponding oxidation of aldehyde, so-called Pinnick oxidation, the good functional group tolerance and the use of inexpensive reagents are the advantages of this protocol.
- Mohamed, Magdi A.,Yamada, Ken-ichi,Tomioka, Kiyoshi
-
experimental part
p. 3436 - 3438
(2009/09/25)
-
- Copper-catalyzed synthesis of five-membered heterocycles via double C-N bond formation: an efficient synthesis of pyrroles, dihydropyrroles, and carbazoles
-
An efficient copper-catalyzed double C-N bond forming reaction using diiodides and nitrogen-centered nucleophiles including amides and carbamates is reported. The reactions proceed to afford di- or tri-substituted N-acylpyrroles, dihydropyrroles, and carbazoles in good to excellent yields when different diiodides such as 1,4-diiodo-1,3-butadienes, 1,4-dihalobut-1-enes, and 2,2′-diiodobiphenyls were employed, respectively. It is crucial to use CuI as the catalyst with the assistance of proper base and diamine ligand.
- Li, Ende,Xu, Xiaobing,Li, Hongfeng,Zhang, Huimin,Xu, Xiaolei,Yuan, Xiyuan,Li, Yanzhong
-
scheme or table
p. 8961 - 8968
(2009/12/24)
-
- Microwave-assisted synthesis of amides from various amines and benzoyl chloride under solvent-free conditions: A rapid and efficient method for selective protection of diverse amines
-
A number of structurally diverse amides were synthesized by reaction of the corresponding amines with benzoyl chloride under microwave irradiation. The proposed procedure ensures short reaction time, high yields, and excellent selectivity and considerably broadens the series of amines as compared to the microwave-assisted synthesis of amides directly from carboxylic acids. It can also be used for selective protection of various amines, including aromatic, aliphatic, and heterocyclic.
- Li, Yanqiu,Wang, Yulu,Wang, Jinye
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p. 358 - 361
(2008/12/22)
-
- Highly efficient copper-catalyzed amidation of aldehydes by C-H activation
-
We have developed a highly efficient method for the copper-catalyzed amidation of aldehydes in the presence of N-bromosuccinimide (NBS). This method is simple, economical, and has practical advantages for synthesis of imides.
- Wang, Long,Fu, Hua,Jiang, Yuyang,Zhao, Yufen
-
experimental part
p. 10722 - 10726
(2009/12/03)
-
- Aerobic photooxidation of benzylamide in the presence of catalytic iodine
-
Benzylamides were found to be oxidized to the corresponding imides in the presence of molecular oxygen and catalytic iodine under photoirradiation. Georg Thieme Verlag Stuttgart.
- Nakayama, Hiroki,Itoh, Akichika
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p. 675 - 678
(2008/12/20)
-
- Conversion of N-Acyl amino acids into imides via oxidative decarboxylation induced by Ag+/Cu2+/S2O8 2- in water
-
N-Acyl amino acids can be converted by oxidative decarboxylation induced by Ag+/Cu2+/S2O82- at room temperature in water into imides in 24-89% yields. Both N-benzoylvaline and N-benzoylleucine gave N-
- Huang, Wenhua,Wang, Meiling,Yue, Hong
-
p. 1342 - 1344
(2008/12/21)
-
- Efficient amidation from carboxylic acids and azides via selenocarboxylates: Application to the coupling of amino acids and peptides with azides
-
(Chemical Equation Presented) A facile one-pot procedure for the coupling of carboxylic acid and azide via selenocarboxylate and selenatriazoline has been developed and successfully applied to the coupling of amino acids and peptides with azides. Selenocarboxylates are readily prepared by the reaction of the activated carboxylic acids with LiAlHSeH under mild conditions. The Selenocarboxylates formed in situ are used to react directly with azides to form the corresponding amides via a selenatriazoline intermediate. Excellent yields were obtained for electron-deficient azides, and moderate to good yields were obtained for electron-rich azides. The selenocarboxylate/azide amidation reaction is clean and chemoselective. It provides an attractive alternative method to the conventional acylation of amines when an amide bond needs to be formed without going through an amine intermediate.
- Wu, Xinghua,Hu, Longqin
-
p. 765 - 774
(2007/10/03)
-
- Copper-catalyzed double N-alkenylation of amides: An efficient synthesis of di- or trisubstituted N-acylpyrroles
-
(Chemical Equation Presented) An efficient copper-catalyzed double alkenylation of amides with (1Z,3Z)-1,4-diiodo-1,3-dienes is reported for the first time. The reactions proceed to afford di- or trisubstituted N-acylpyrroles in good to excellent yields using CuI as the catalyst, Cs2CO 3 as the base, and rac-trans-N,N′-dimethylcyclohexane-1,2- diamine as the ligand.
- Yuan, Xiyuan,Xu, Xiaobing,Zhou, Xiaobo,Yuan, Jiwei,Mai, Lugen,Li, Yanzhong
-
p. 1510 - 1513
(2007/10/03)
-
- Improved solubility and stability of trialkylammonium selenocarboxylate in organic solvents for efficient amidation with azides
-
Trialkylammonium selenocarboxylate, formed in situ from the reaction of diacyl diselenide with piperidine in the presence of diisopropylethylamine, was found to react readily at room temperature with electron-deficient azides to form amides in excellent yields. The trialkylammonium selenocarboxylate salt formed has good solubility and stability in organic solvents. The enhanced stability allowed mild heating to improve the amidation yields with electron-rich azides.
- Surabhi, Prathima,Wu, Xinghua,Hu, Longqin
-
p. 4609 - 4613
(2007/10/03)
-
- Oxidative photo-decarboxylation in the presence of mesoporous silicas
-
FSM-16, a mesoporous silica, was found to catalyze oxidative photo-decarboxylation of α-hydroxy carboxylic acid, phenyl acetic acid derivatives and N-acyl-protected α-amino acids to afford the corresponding carbonyl compounds. Furthermore, FSM-16 proved to be re-usable by re-calcination at 450°C after the reaction.
- Itoh, Akichika,Kodama, Tomohiro,Masaki, Yukio,Inagaki, Shinji
-
p. 1571 - 1575
(2007/10/03)
-
- Ceric ammonium nitrate promoted oxidation of oxazoles
-
The ceric ammonium nitrate promoted oxidations of 4,5-diphenyloxazoles and oxazoles with various substitution patterns have been investigated. This transformation results in the formation of the corresponding imide in good yield and tolerates a wide variety of functional groups and substituents on the oxazole moiety.
- Evans, David A.,Nagorny, Pavel,Xu, Risheng
-
p. 5669 - 5671
(2007/10/03)
-
- Synthesis of imides, N-acyl vinylogous carbamates and ureas, and nitriles by oxidation of amides and amines with dess-martin periodinane
-
Expanding our synthetic tool repertoire: The DMP-mediated oxidation of a range of amide substrates has been demonstrated, affording the corresponding imides and N-acyl vinylogous carbamates and ureas. Likewise, an array of benzylic and related amines have also been successfully converted into their nitrile counterparts (see scheme; DMP = Dess-Martin periodinane). (Chemical Equation Presented)
- Nicolaou,Mathison, Casey J. N.
-
p. 5992 - 5997
(2007/10/03)
-
- Aerobic oxidation with N-hydroxyphthalimide catalysts in ionic liquid
-
N-Hydroxyphthalimide (NHPI)-catalyzed aerobic oxidations in the ionic liquids were examined for the first time. Both NHPI and its ionic derivative, 3-pyridinylmethyl-N-hydroxyphthalimide (Py-NHPI), were found to have better performance in the ionic liquid than in the conventional organic solvents for the aerobic oxidation of N-alkylamides to imides. On the other hand, Py-NHPI was found to be a much better catalyst than NHPI for the aerobic oxidation of benzylic compounds in the ionic liquid.
- Wang, Jia-Rui,Liu, Lei,Wang, Ye-Feng,Zhang, Ying,Deng, Wei,Guo, Qing-Xiang
-
p. 4647 - 4651
(2007/10/03)
-
- Studies on the reactivity pattern of in situ generated tetraethylammonium superoxide with 2-oxazolin-5-ones
-
A variety of 2-oxazolin-5-ones have been allowed to react under the mild reaction conditions of potassium superoxide and tetraethylammonium bromide in dry dimethylformamide at room temperature. Different products are obtained depending on the substituents attached to the C-4 position.
- Singh, Krishna Nand,Kumar, Rajesh
-
p. 381 - 386
(2007/10/03)
-
- Novel chromium(VI) catalyzed oxidation of N-alkylamides to imides with periodic acid
-
A novel and practical procedure for preparation of imides is described using chromium(VI) oxide to catalyze the oxidation of N-alkylamides with periodic acid in the presence of acetic anhydride in acetonitrile.
- Xu, Liang,Zhang, Suhong,Trudell, Mark L.
-
p. 1668 - 1669
(2007/10/03)
-
- An easy method for the generation of amides from ketones by a Beckmann type rearrangement mediated by microwave
-
A facile and efficient procedure is developed for one-pot synthesis of amides from ketones in the presence of P2O5/SiO 2 reagent in dry media under microwave irradiation. Ketoximes indirectly in the same conditions gave amides by Beckmann rearrangement.
- Eshghi, Hossein,Gordi, Zinat
-
p. 2971 - 2978
(2007/10/03)
-
- The 1,2,4-triazolyl cation: Thermolytic and photolytic studies
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The generation of the 1,2,4-triazolyl cation (1) has been attempted by the thermolysis and photolysis of 1-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridinium tetrafluoroborate (2) and the thermolysis of 1- and 4-diazonium-1,2,4-triazoles, using mainly mesitylene as the trapping agent. Thermolysis of 2 gave mostly 1,2,4-triazole, together with 3-(1,2,4-triazol-4-yl)-2,4,6-trimethylpyridine, 4-(1,2,4-triazol-4-ylmethyl)-2,6-dimethylpyridine, and 4-(2,4,6-trimethylbenzyl)-2,6-dimethylpyridine. Thermolysis, of each of the diazonium salts in the presence of mesitylene again gave mainly triazole together with very low yields of 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene and the corresponding -4-yl isomer in about the same ratio. On the other hand, photolysis of 2 in mesitylene gave mainly 1-(1,2,4-triazol-1-yl)-2,4,6-trimethylbenzene. A photoinduced electron transfer from mesitylene to 2 has been observed and preliminary laser flash photolyses of 2 and the corresponding 2,4,6-triphenylpyridinium salt have been carried out. The observed transients are explained as arising from the first excited states of the pyridinium salts rather than from 1. Ab initio MO calculations are reported and indicate that the predicted electronic ground-state of the triazolyl cation is a triplet state of B1 symmetry with five π electrons, which corresponds to a diradical cation (1c). Possible mechanisms for the formation of the various products are proposed.
- Abramovitch,Beckert,Gibson Jr.,Belcher,Hundt,Sierra,Olivella,Pennington,Sole
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p. 1242 - 1251
(2007/10/03)
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- New Synthetic Method of Imides through Oxidative Photodecarboxylation Reaction of N-Protected α-Amino Acids with FSM-16
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FSM-16, a mesoporous silica, was found to promote the oxidative photodearboxylation of N-acyl-protected α-amino acids in hexane to afford the corresponding imides.
- Itoh, Akichika,Kodama, Tomohiro,Inagaki, Shinji,Masaki, Yukio
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p. 542 - 543
(2007/10/03)
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- Laser flash photolysis of aziridines. Spectroscopic and kinetic characterization of azomethine ylides. Their [3 + 2] cyclization with alkenes and protonation by water-alcohols to yield iminium ions
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The reactive intermediates generated by laser flash photolysis (λexc = 248 or 193 nm) of the aziridines (E)-1-butyl-2,3-diphenylaziridine 1, (E)-2,3-diphenylaziridine 2, 1,2-diphenylaziridine 3, 1-(p-methoxyphenyl)-2-phenylaziridine 4 and 1-butyl-2-phenylaziridine 5 in acetonitrile and alcohols as solvents were identified as the corresponding azomethine ylides and spectroscopically and kinetically characterized. The rate constants for the [3 + 2] reaction of the ylides with electron-deficient alkenes to give pyrrolidines are between 106 and 109 M-1 s-1. In the case of 1 and 2 iminium ions are produced by protonation (by H2O or ROH) of the ylides (also studied by time-resolved conductance). For this reaction, with MeOH as the proton donor, the kinetic isotope effect is k(MeO-H)/ k(MeO-D) = 5-7, from which it is concluded that the transition state for protonation of the carbanionic site of the ylide is linear.
- Gaebert, Carsten,Siegner, Christian,Mattay, Jochen,Toubartz, Marion,Steenken, Steen
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p. 2735 - 2739
(2007/10/03)
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- Self-addition products from the alkylation of amino acid-derived oxazolidinones: X-ray molecular structures of (2R,4S,1′S)-3-benzoyl-4-[benzoylamino(phenyl)methyl]-4-benzyl-2-phenyl-1, 3-oxazolidin-5-one, (2A,45,1′S)- and (2R,4S,1′R)-3-benzoyl-4-[benzoylamino(phenyl)methyl]-4-isopropyl-2-phenyl- 1,3-oxazolidin-5-one
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The alkylation of (2R,4S)-3-benzoyl-4-benzyl-2-phenyloxazolidin-5-one 7 with diphenylmethyl bromoacetate proceeded with high diastereoselectivity, and the resulting product was hydrolysed to give [(2′R,4′5)-3′-benzoyl-4′-benzyl-5′-oxo-2′- phenyloxazolidin-4′-yl]acetic acid 9. The self-addition by-product (2R,45,1′S)-3-benzoyl-4-[benzoylamino(phenyl)methyl]-4-benzyl-2-phenyl-1, 3-oxazolidin-5-one 11 was also isolated. The structures of compound of 11 and the related self-addition products (2R,4S,1′S and 1′R)-3-benzoyl-4-[benzoylamino(phenyl)methyl]-4-isopropyl-2-phenyl-1,3- oxazolidin-5-one 20 and 21 were determined by X-ray crystallography. The mechanism of formation of the self-addition products is discussed.
- Abell, Andrew D.,Taylor, Jane M.,Oldham, Mark D.
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p. 1299 - 1304
(2007/10/03)
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- Incorporation of Molecular Nitrogen Into Organic Compounds. Titanium Catalyzed Nitrogenation
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Incorporation of molecular nitrogen into organic compounds was realized using a catalytic amount of TiCl4 in the presence of excess TMSCl and Li.Various imides were prepared from the corresponding acid anhydrides by use of this catalytic system.
- Mori, Miwako,Kawaguchi, Mami,Hori, Masanori,Hamaoka, Shin-ichi
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p. 729 - 740
(2007/10/02)
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- Photoinduced β-Elimination of the Triazole Group in the 1-(N,N-Bisacyl)amino-1,2,3-triazoles
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The photoelimination of the 1,2,3-triazole group from the title compounds proseeds, depending upon the reaction conditions, via an intra- or intermolecular hydrogen abstraction or electron-transfer mechanism, followed by homolytic cleavage of the N,N bond.It can also proceed via ?*-assisted β-cleavage of the same weak bond, when light of shorter wavelenght is used.The composition of the products suggests that in all cases most probably a ?-type 1,2,3-triazolyl radical 10 is eliminated which is further quenched by hydrogen or chlorine abstraction.
- Kalambokis, E.A.,Maroulis, A.J.,Alexandrou, N.E.
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p. 1301 - 1308
(2007/10/02)
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- Incorporation of molecular nitrogen into organic compounds. Titanium catalyzed nitrogenation
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Incorporation of molecular nitrogen into organic compounds was realized using a catalytic amount of TiCl4 in the presence of excess TMSCl and Li under nitrogen.
- Kawaguchi, Mami,Hamaoka, Shin-Ichi,Mori, Miwako
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p. 6907 - 6910
(2007/10/02)
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- A novel Dieckmann-type cyclization, the final step of the synthesis of a carbacephem derivative
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The treatment of the triacylamine, methyl 4-(dibenzoyl-aminocarbonylethyl)-2-oxoazetidine-1-acetate (2), with sodium bis(trimethylsilyl)amide leads to an unprecedented Dieckmann-type ring closure to form the anion of the carbacephem derivative, methyl 3-hydroxy-1-carbacephem-4-carboxylate, (3).
- Neyer,Ugi
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p. 743 - 744
(2007/10/02)
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