- Resolution of Enantiomers of Novel C2-Symmetric Aminobisphosphinic Acids via Diastereomeric Salt Formation With Quinine
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C2-symmetric N,N-bis(phosphinomethyl)amines were prepared by the thermal reaction of aromatic aldehydes with ammonia and hypophosphorus acid as previously described. Both enantiomers of C2-symmetric N,N-bis(phosphinomethyl)amine were obtained in a high enantiomeric purity through the diastereomeric salt formation with (-)-quinine, and subsequent fractional crystallization. X-ray crystallographic analysis of one of the diastereomeric salts clearly revealed that (-)-quinine could be an efficient resolving agent for obtaining the single enantiomer (R,R)-N,N-bis(phosphinomethyl)amine.
- Kaboudin, Babak,Faghihi, Mohammad-Reza,Kazemi, Foad,Yokomatsu, Tsutomu
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- Reactions of dialkyl phosphonates and phosphinates with bis(benzylideneimino)toluene
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Dialkyl phosphonates bind to the C=N bond of bis(benzylideneimino)toluene, with formation of dialkyl (benzylideneimino)benzylaminobenzyl phosphonates. The complicated character of IR spectra of these compounds is connected with the possibility of formation of dimeric cyclic associates and intramolecular hydrogen bonding. Phosphinic acid reacts with bis(benzylidenimino)toluene in a 2 : 1 ratio to afford N,N′-benzylidenebis(α-amino-benzylphosphonic) acid.
- Pudovik,Shagidullin,Khairullin,Vandyukova,Chernova,Gainullin,Pudovik
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Read Online
- Design, synthesis of novel celastrol derivatives and study on their antitumor growth through HIF-1α pathway
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Four series of hypoxia-inducible factor-1 alpha (HIF-1α) functioning derivatives stemming from modifications to the C-29 carboxyl group of celastrol were designed and synthesized, and their anticancer activities were evaluated. To address the structure and activity relationship of each derivative, extensive structural changes were made. HRE luciferase reporter assay demonstrated that 12 modified compounds showed superior HIF-1α inhibitory activity. Among them, compound C6 exhibited the best features: firstly, the strongest HIF-1α inhibitory activity (IC50 = 0.05 μM, 5-fold higher than that of celastrol); secondly, lower cytotoxicity (22-fold lower, C6-16.85 μM vs celastrol-0.76 μM). Thus, the safety factor of C6 was about 112 times higher than that of celastrol. Western blot assay indicated that C6 may inhibit the expression of HIF-1α protein in cells. Additionally, C6 hindered tumor cell cloning, migration and induced cell apoptosis. It is worth mentioning that in the mouse tumor xenograft model, C6 (10 mg/kg) displayed good antitumor activity in vivo, showing a better inhibition rate (74.03%) than the reference compound 5-fluorouracil (inhibition rate, 59.58%). However, the celastrol treatment group experienced collective death after four doses of the drug. Moreover, C6 minimally affected the mouse weight, indicating that its application in vivo has little toxic effect. H&E staining experiments show that it could also exacerbate the degree of tumor cell damage. The results of water solubility experiment show that the solubility of C6 is increased by 1.36 times than that of celastrol. In conclusion, C6 is a promising antitumor agent through HIF-1α pathway.
- Shang, Fan-Fan,Wang, Jing Ying,Xu, Qian,Deng, Hao,Guo, Hong-Yan,Jin, Xuejun,Li, Xiaoting,Shen, Qing-Kun,Quan, Zhe-Shan
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- Synthesis of β-Phosphinolactams from Phosphenes and Imines
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Various cis-β-phosphinolactams are synthesized stereoselectively for the first time from imines and diazo(aryl)methyl(diaryl)phosphine oxides under microwave irradiation. Diazo(aryl)methyl(diaryl)phosphine oxides first undergo the Wolf rearrangement to generate phosphenes. Imines nucleophilically attack the phosphenes followed by an intramolecular nucleophilic addition via less steric transition states to give final cis-β-phosphinolactams. C-Styrylimines generally give rise to β-phosphinolactams in higher yields than C-arylimines. The stereoselectivity and proposed mechanism are rationalized by DFT theoretical calculation.
- Fu, Xingyang,Li, Xinyao,Xu, Jiaxi
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supporting information
p. 8733 - 8737
(2021/11/17)
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- Platinum Nanoparticles Uniformly Dispersed on Covalent Organic Framework Supports for Selective Synthesis of Secondary Amines
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Covalent organic frameworks (COFs) with pore structures are talented supports for active components. In this report, COF has been rationally fabricated and served as host for growing uniformly dispersed platinum nanoparticles with a narrow size distribution (2 nm). The obtained hybrid Pt/COF exhibits high catalytic activity in the reductive amination of benzaldehyde towards secondary amines with a yield of 96 % and good recyclability. The preferable selectivity towards secondary amines could be attributed to synergistic effects of active platinum nanoparticles and COF, in which metallic Pt nanoparticles were uniformly dispersed with a positively charged surface. This work will open an avenue towards controlling the interaction between active metals and support as well as rational design of catalysts for demanding transformations for fine agrochemicals intermediates.
- Li, Xinjun,Liu, Jianguo,Ma, Longlong,Tang, Long,Wang, Chenguang,Wang, Nan
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- A Journey from Thermally Tunable Synthesis to Spectroscopy of Phenylmethanimine in Gas Phase and Solution
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Phenylmethanimine is an aromatic imine with a twofold relevance in chemistry: organic synthesis and astrochemistry. To tackle both aspects, a multidisciplinary strategy has been exploited and a new, easily accessible synthetic approach to generate stable imine-intermediates in the gas phase and in solution has been introduced. The combination of this formation pathway, based on the thermal decomposition of hydrobenzamide, with a state-of-the-art computational characterization of phenylmethanimine laid the foundation for its first laboratory observation by means of rotational electric resonance spectroscopy. Both E and Z isomers have been accurately characterized, thus providing a reliable basis to guide future astronomical observations. A further characterization has been carried out by nuclear magnetic resonance spectroscopy, showing the feasibility of this synthetic approach in solution. The temperature dependence as well as possible mechanisms of the thermolysis process have been examined.
- Melli, Alessio,Potenti, Simone,Melosso, Mattia,Herbers, Sven,Spada, Lorenzo,Gualandi, Andrea,Lengsfeld, Kevin G.,Dore, Luca,Buschmann, Philipp,Cozzi, Pier Giorgio,Grabow, Jens-Uwe,Barone, Vincenzo,Puzzarini, Cristina
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supporting information
p. 15016 - 15022
(2020/10/19)
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- Concurrent Formation of N-H Imines and Carbonyl Compounds by Ruthenium-Catalyzed C-C Bond Cleavage of β-Hydroxy Azides
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A commercial cyclopentadienylrutenium dicarbonyl dimer ([CpRu(CO)2]2) efficiently catalyzes the formation of N-H imines and carbonyl compounds simultaneously from β-hydroxy azides via C-C bond cleavage under visible light. Density functional theory calculations for the cleavage reaction support the mechanism involving chelation of alkoxy azide species and liberation of nitrogen as the driving force. The synthetic utility of the reaction was demonstrated by a new amine synthesis promoted by chemoselective allylation of imine and synthesis of isoquinoline.
- Lee, Jeong Min,Bae, Dae Young,Park, Jin Yong,Jo, Hwi Yul,Lee, Eunsung,Rhee, Young Ho,Park, Jaiwook
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p. 4608 - 4613
(2020/06/05)
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- Stereoselective Synthesis of α,α′-Dihydroxy-β,β′-diaryl-β-amino Acids by Mannich-Like Condensation of Hydroarylamides
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Dual α,α′-Dihydroxy-β-amino acids are highly interesting tools for several industrial applications. Nevertheless, only few derivatives are reported in the literature and knowledge concerning the substitution pattern as well as their enantioselective syntheses are lacking. Herein, we report on the preparation of enantiopure α,α′-dihydroxy-β,β′-diaryl-β-amino acid (dual) derivatives by an efficient Mannich-like condensation of hydroarylamides with 5,6-diethoxy-5,6-dimethyl-1,4-dioxan-2-one (triethylsilyl)ketene acetal. The synthetic protocol has been optimized affording the dual compounds in very good yields and with different aryl substitution patterns. Taking advantage of the “double stereodifferentiation” concept, a highly stereoselective reaction was performed: of the 16 possible isomers, only two diastereoisomers (d.r. up to 93:7) formed. Insights into the high stereocontrol of this condensation were given.
- Pecnikaj, Ilir,Foschi, Francesca,Bucci, Raffaella,Gelmi, Maria Luisa,Castellano, Carlo,Meneghetti, Fiorella,Penso, Michele
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supporting information
p. 6707 - 6713
(2019/11/03)
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- Adducts of Triallylborane with Ammonia and Aliphatic Amines as Stoichiometric Allylating Agents for Aminoallylation Reaction of Carbonyl Compounds
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Triallylborane-amines adducts are effective stoichiometric allylating agents in the aminoallylation reaction of carbonyl compounds in methanol. Moreover, copper-catalyzed diastereoselective allylation of Ellman's imine was achieved with triallylborane-methylamine adduct.
- Kuznetsov, Nikolai Yu.,Tikhov, Rabdan M.,Strelkova, Tatiana V.,Bubnov, Yuri N.
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supporting information
p. 3549 - 3552
(2018/06/26)
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- Novel α,β-unsaturated amide derivatives bearing α-amino phosphonate moiety as potential antiviral agents
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Based on flexible construction and broad bioactivity of ferulic acid, a series of novel α,β-unsaturated amide derivatives bearing α-aminophosphonate moiety were designed, synthesized and systematically evaluated for their antiviral activity. Bioassay results indicated that some compounds exhibited good antiviral activities against cucumber mosaic virus (CMV) and tobacco mosaic virus (TMV) in vivo. Especially, compound g18 showed excellent curative and protective activities against CMV, with half-maximal effective concentration (EC50) values of 284.67 μg/mL and 216.30 μg/mL, which were obviously superior to that of Ningnanmycin (352.08 μg/mL and 262.53 μg/mL). Preliminary structure-activity relationships (SARs) analysis revealed that the introduction of electron-withdrawing group at the 2-position or 4-position of the aromatic ring is favorable for antiviral activity. Present work provides a promising template for development of potential inhibitor of plant virus.
- Lan, Xianmin,Xie, Dandan,Yin, Limin,Wang, Zhenzhen,Chen, Jin,Zhang, Awei,Song, Baoan,Hu, Deyu
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p. 4270 - 4273
(2017/09/12)
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- Selective Hydrogenation of Nitriles to Secondary Imines Catalyzed by an Iron Pincer Complex
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Selective hydrogenation of nitriles to secondary imines catalyzed by an iron complex, the pincer complex (iPr-PNP)Fe(H)Br(CO), in the presence of catalytic base, is reported. A wide range of (hetero)aromatic and aliphatic nitriles are hydrogenated to the corresponding secondary imines under mild conditions.
- Chakraborty, Subrata,Milstein, David
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p. 3968 - 3972
(2017/06/19)
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- A Mild TEMPO-Catalyzed Aerobic Oxidative Conversion of Aldehydes into Nitriles
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An efficient method to prepare nitriles from aldehydes using hexamethyldisilazane (HMDS) as the nitrogen source has been developed. The reactions were performed with 2,2,6,6-tetramethylpiperidine l-oxyl (TEMPO) as the catalyst, NaNO2 or TBN as the co-catalyst, and molecular oxygen as the terminal oxidant under mild conditions. A variety of aromatic, heteroaromatic, aliphatic and allylic aldehydes could be converted into their corresponding nitriles in good to excellent yields.
- Fang, Chaojie,Li, Meichao,Hu, Xinquan,Mo, Weimin,Hu, Baoxiang,Sun, Nan,Jin, Liqun,Shen, Zhenlu
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p. 1157 - 1163
(2016/04/19)
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- Deep eutectic solvent catalyzed eco-friendly synthesis of imines and hydrobenzamides
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The urea-choline chloride-based deep eutectic solvent was found to be an efficient catalyst and reaction media for the additive-free synthesis of imines (Schiff bases) and hydrobenzamides by the reaction of aldehydes with amines and ammonia in good to high yields. Outstanding features of this protocol were the general and atom-economical reaction, absence of external catalysts and additives, simple workup, and availability and recycling of urea-choline chloride as a green solvent. Graphical abstract: (Chemical Equation Presented).
- Azizi, Najmedin,Edrisi, Mahtab
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p. 1695 - 1698
(2015/09/21)
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- Catalytic asymmetric 1,2-addition of α-isothiocyanato phosphonates: Synthesis of chiral β-hydroxy- or β-amino-substituted α-amino phosphonic acid derivatives
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α-Amino phosphonic acid derivatives are considered to be the most important structural analogues of α-amino acids and have a very wide range of applications. However, approaches for the catalytic asymmetric synthesis of such useful compounds are very limited. In this work, simple, efficient, and versatile organocatalytic asymmetric 1,2-addition reactions of α-isothiocyanato phosphonate were developed. Through these processes, derivatives of β-hydroxy-α-amino phosphonic acid and α,β-diamino phosphonic acid, as well as highly functionalized phosphonate-substituted spirooxindole, can be efficiently constructed (up to 99 % yield, d.r. >20:1, and >99 % ee). This novel method provides a new route for the enantioselective functionalization of α-phosphonic acid derivatives. Correct chirality critical: Organocatalytic asymmetric Adol-type and Mannich-type reactions of α-isothiocyanato phosphonate have been realized. Michael addition was also applicable under the same catalytic conditions. This versatile approach provides a new route for the synthesis of diverse highly optically active functionalized α-amino phosphonic acid derivatives. Copyright
- Cao, Yi-Ming,Shen, Fang-Fang,Zhang, Fu-Ting,Zhang, Jin-Long,Wang, Rui
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supporting information
p. 1862 - 1866
(2014/03/21)
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- Cyclopalladation and reactivity of amino esters through C - H bond activation: Experimental, kinetic, and density functional theory mechanistic studies
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The orthopalladation, through C - H bond activation, of a large number of amino esters and amino phosphonates derived from phenylglycine, and having different substituents at the aryl ring and the C-α atom, as well as on the N-amine atom, has been studied. The experimental observations indicated an improvement in the yields of the orthopalladated compounds when the N-amine and/or the C-α atom are substituted, when compared with the unsubstituted methyl phenylglycinate derivatives. In contrast, substitutions at the aryl ring do not promote significant changes in the orthometalation results. Furthermore, the use of hydrochloride salts of the amino esters has also been shown to have a remarkably favorable effect on the process. All these observations have been fully quantified at different temperatures and pressures by a detailed kinetic study in solution in different solvents and in the presence and absence of added Bronsted acids and chloride anions. The data collected indicate relevant changes in the process depending on these conditions, as expected from the general background known for cyclopalladation reactions. An electronic mechanism of the orthopalladation has been proposed based on DFT calculations at the B3LYP level, and a very good agreement between the trends kinetically measured and the theoretically calculated activation barriers has been obtained. The reactivity of the new orthopalladated amino phosphonate derivatives has been tested and it was found that their halogenation, alkoxylation and carbonylation resulted in formation of the corresponding functionalized ortho- haloaminophosphonates, ortho-alkoxyaminophosphonates and oxoisoindolinylphosphonates. Remote control: The orthopalladation, through C - H bond activation, of substituted amino esters and amino phosphonates derived from phenylglycine has been studied (see scheme). Determination of the reaction rates indicated a clear acceleration of the C - H activation rate when the n-amine and/or the C-α atom are substituted. Substitutions at the aryl ring do not promote changes. The use of hydrochloride salts of the amino esters also has a strong accelerating effect on the process.
- Laga, Eduardo,Garcia-Montero, Angel,Sayago, Francisco J.,Soler, Tatiana,Moncho, Salvador,Cativiela, Carlos,Martinez, Manuel,Urriolabeitia, Esteban P.
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supporting information
p. 17398 - 17412
(2014/01/06)
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- Synthesis and bioactivities of α-aminophosphonate derivatives containing benzothiazole and thiourea moieties
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The synthesis of a series of novel α-aminophosphonate derivatives containing benzothiazole and thiourea moieties from substituted 2-aminobenzothiazoles and synthetic intermediates O,O'-dialkylisothiocyanat- (phenyl)methylphosphonates under microwave irradiation has been demonstrated. Several salient features, such as good to excellent yields, shorter reaction times, milder reaction conditions, and simple purification procedures, make the present synthetic protocol highly attractive to access the title compounds. Bioassays indicated that most of the compounds possessed broad-spectrum insecticidal and antiviral activities against Tobacco Mosaic Virus (TMV) in vivo. Interestingly, in comparison with control insecticide Avermectin, two compounds displayed remarkably high in vitro insecticidal activities against Plutella xylostella. Furthermore, according to the results from preliminary bioassay, all were associated with moderate to good anti-TMV activities. [Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Tables S1-S4. Figures S1-S52.] Copyright Taylor and Francis Group, LLC.
- Liu, Jing-Zi,Song, Bao-An,Bhadury, Pinaki S.,Hu, De-Yu,Yang, Song
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scheme or table
p. 61 - 70
(2012/04/10)
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- Novel method for the synthesis of α-amino-α- hydroxyalkylphosphinic acids and bis(α-aminoalkyl)phosphinic acids: Nuclephilic addition of α-hydroxy-H-phosphinic acids to diimines
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We report here a novel and simple method for the synthesis of α-amino-α-hydroxyalkylphosphinic acids in good yields in two simple steps without any protection-deprotection steps. We have developed an efficient method for the synthesis of α-amino-α-hydroxyalkylphosphinic acids via the reaction of easily available α-hydroxyalkylphosphinic acids with diimines. Treatment of α-hydroxyalkylphosphinic acids with diimines in the presence of trimethylsilyl chloride (TMSCl) gives α-amino-α- hydroxyalkylphosphinic acids in good yields. The reaction gave a mixture of two diastereomeric forms of α-amino-α-hydroxyalkylphosphinic acids. The difference in solubility in organic solvents allowed us to readily separate the diastereoisomers. Georg Thieme Verlag Stuttgart · New York.
- Kaboudin, Babak,Haghighat, Hamideh,Alaie, Saied,Yokomatsu, Tsutomu
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supporting information; experimental part
p. 1965 - 1969
(2012/09/22)
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- Catalyst-free synthesis of α-aminoacylamides via n,n'- bis(phenylmethylidene) phenylmethanediamine as imine surrogate in ugi multicomponent reaction
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A novel one-pot, multicomponent, and catalyst-free reaction of N,N'-bis (phenylmethylidene) phenylmethane, carboxylic acids, and isocyanides yielding α-aminoacyl-amides is described. The reaction is based on the combination of an Ugi three-component reaction followed by hydrolysis. Taylor & Francis Group, LLC.
- Alizadeh, Abdolali,Mokhtari, Javad
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experimental part
p. 686 - 693
(2011/12/21)
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- Synthesis of the novel pyrimido[1,6-a]pyrimidine and imidazo[1,2-c] pyrimidine derivatives based on heterocyclic ketene aminals
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A concise and efficient route for the synthesis of pyrimido[1,6-a] pyrimidines and imidazo[1,2-c]pyrimidines by simply refluxing a reaction mixture of different heterocyclic ketene aminals and N,N′-bis(arylmethylidene) arylmethane was developed. This protocol provides an alternative method for application in combinatorial and parallel synthesis in drug discovery.
- Alizadeh, Abdolali,Mokhtari, Javad,Ahmadi, Mehdi
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experimental part
p. 319 - 322
(2012/01/05)
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- Synthesis and cytotoxicity of O,O′-dialkyl {[2-(substituted phenoxy)acetamido](substituted phenyl)methyl}phosphonates
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A series of O,O′-dialkyl {[2-(substituted phenoxy)acetamido] (substituted phenyl)methyl}phosphonates was synthesized and their cytotoxic activities were tested against various human tumor cell lines. Some compounds (5q, 5r, 5s, 5w, 5x and 5y) showed relatively high cytotoxicity. Especially, compounds 5x and 5q exhibited the best cytotoxicity against KB and CNE2 cells with IC50 7.1 and 11.4 μM, respectively. Their inhibitory activities against KB and CNE2 cells were even higher than that of fluorouracil.
- Ning, Lihong,Wang, Wei,Liang, Yongju,Peng, Hao,Fu, Liwu,He, Hongwu
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experimental part
p. 379 - 384
(2012/03/13)
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- Bis{phenyl[di(methoxyethyloxy)phosphoryl]methyl}amine as a new ligand for metal ions and cationic organic molecules
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The bis(phenylphosphorylmethyl)amine containing binding units based on "crown-ether like" ester moiety was tested as a supramolecular host molecule. The complexation properties towards metal ions (Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Ba2+) and hydrochlorides of amino acids (Lys, Arg), diethylenetriamine (2EN3A) and pentaethylenehexaamine (5EN6A) were studied. In order to assess the binding affinities of the receptor to selected guest molecules in various solvents, the ESI-MS and NMR techniques were applied. The results were also supported by theoretical studies. The ESI-MS studies revealed the selective binding of Cs+ and 5EN6 by the phosphonate molecule, whereas NMR investigation in solution indicated tighter association of the host-guest system obtained for Mg2+ and Arg. The discrepancies between the results originating from both used methods are most likely caused by influence of the solvent on intermolecular interactions.
- M?ynarz, Piotr,Ptak, Tomasz,Czernicka, Anna,Pankiewicz, Rados?aw,Gluza, Karolina,Zarzeczańska, Dorota
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experimental part
p. 18 - 23
(2011/05/04)
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- Synthesis and antiviral activity of novel pyrazole amides containing α-aminophosphonate moiety
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A series of novel pyrazole amides J1-J15 containing an α-aminophosphonate moiety were synthesized and subsequently characterized by spectral (IR, 1H-, 13C-, 31P-, and 19F-NMR) data and elemental analysis. The racemic sample of J1 was further separated into its enantiomers under normal-phase condition on two immobilized polysaccharide-based chiral stationary phases (Chiralpak IA and Chiralpak IC). The synthesized compounds revealed certain degree of antiviral activity in the bioassay. The title compounds (J 3, J10, and J12) showed some curative activities (39.9%, 41.8%, 50.1%, respectively) against tobacco mosaic virus at 0.5 mg/mL.
- Wu, Lintao,Song, Baoan,Bhadury, Pinaki S.,Yang, Song,Hu, Deyu,Jin, Linhong
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scheme or table
p. 389 - 396
(2011/06/20)
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- Synthesis and biological evaluation of novel phosphonates derivatives of as potential antitumor agents
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A series of dialkyl [2-(4,6-dimethoxypyrimidin-2-yloxy)benzamido](aryl) methylphosphonates derivatives were designed and synthesized. All the new compounds were identified by elemental analysis, IR, 1H NMR, 31P NMR, and MS. Their antitumor activity against KB and CNE1 cells was examined. Some of the compounds showed potential antitumor activity, which provided some hints for further study of structure modification. In particular, the compounds 6i and 6j displayed more potent cytotoxic activities against KB in comparison with 5-FU. Copyright Taylor & Francis Group, LLC.
- Jin, Chuanfei,Liang, Yong-Ju,He, Hongwu,Fu, Liwu
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experimental part
p. 2096 - 2103
(2011/12/01)
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- Synthesis and antiviral bioactivities of novel chiral bis-thiourea-type derivatives containing α-aminophosphonate moiety
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Starting from 1-((1R,2R)-2-aminocyclohexyl)-3-substituted thioureas (3a-c) and substituted isothiocyanates (9a-d), chiral bis-thiourea derivatives containing α-aminophosphonate moiety 10a-l were prepared and completely characterized by elemental analysis, physical and spectral (IR, 1H NMR, 13C NMR, 31P NMR) data. The results of bioassay revealed that compounds 10a and 10e possessed appreciable curative bioactivities on cucumber mosaic virus (CMV) at 0.5 mg/mL in vivo (inhibitory rate = 60.3%, 64.8% respectively) and tobacco mosaic virus (TMV) at 0.5 mg/mL in vivo (inhibitory rate = 50.3%, 50.8% respectively), which were comparable to the values shown by standard reference (58.7%) and commercial product Ningnanmycin (56.3%), respectively. Chiral compound 10e displayed more potent antiviral activity (EC50 = 0.149 mg/mL) than Ningnanmycin (EC50 = 0.201mg/mL) against CMV.
- Yang, Xuan,Song, Baoan,Jin, Linhong,Wei, Xue,Bhadury, S. Pinaki,Li, Xiangyang,Yang, Song,Hu, Deyu
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scheme or table
p. 103 - 109
(2011/12/21)
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- Synthesis and complexation properties of N, N-bis(phosphinomethyl)amine as a new class of 1-aminophosphinic acids with transition metals and lanthanide ions in aqueous solution
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The treatment of aromatic aldehydes with ammonia and hypophosphorus acid gave novel C2-symmetric N,N-bis(phosphinomethyl)amines as a new class of 1-aminophosphinic acid compounds. Complexation properties of N,N-bis(phosphinomethyl)amines with transition metals such as Co2+, Ni2+, Zn2+, Cu2+, and Cd2+ and lanthanide ions La3+ and Gd3+ were studied in aqueous solution by the pH-potentiometric method. Dissociation constants (pK) of the compound were determined by the pH-potentiometric technique. The complexation studies with compound dl-2a showed the best fit of the titration curves were obtained when the ligand-metal stoichiometric ratio was 1:1 and 2:1.
- Kaboudin, Babak,Saadati, Fariba,Golshan, Azadeh,Abdollahi, Hamid,Yokomatsu, Tsutomu
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experimental part
p. 3651 - 3656
(2012/01/06)
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- Beyond click-chemistry: Transformation of azides with cyclopentadienyl ruthenium complexes
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The cyclopentadienyl Ru complexes Cp*RuCl(cod) (cod = 1,5-cyclooctadiene), Cp*RuCl(PPh3)2, and [CpRuCl2]2 (Cp = η5-1-methoxy-2,4-di-tert- butyl-3-neopentylcyclopentadienyl) are able to catalyze the decomposition of benzyl azides to give 1,3,5-triphenyl-2,4-diazapenta-1,4-diene ("hydrobenzamide"), benzyl-benzylideneamine, and benzonitrile. Reactions with the catalyst precursor [CpRuCl2]2 are particularly fast and give hydrobenzamide with high selectivity. A similar coupling reaction is observed for other benzylic azides but not for (2-azidoethyl)benzene and ethyl-4-azidobutanoate. If the reactions are performed in the presence of water, benzylic azides are converted into aldehydes. Mononuclear tetrazene complexes are formed in stoichiometric reactions of [CpRuCl2]2 with benzyl azide and (2-azidoethyl)benzene.
- Risse, Julie,Scopelliti, Rosario,Severin, Kay
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experimental part
p. 3412 - 3418
(2011/08/08)
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- Synthesis and in vitro study of pseudo-peptide thioureas containing α-aminophosphonate moiety as potential antitumor agents
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Twenty pseudo-peptide thioureas IIa-l containing α-aminophosphonate moiety were synthesized from the reaction of chiral α-amino carboxamide derivatives Ia-c with O,O′-dialkylisothiocyanato(phenyl)methylphosphonate 5. The synthesized compounds were completely characterized by elemental analysis, physical and spectral (IR, 1H NMR, 13C NMR) data. According to the preliminary studies on antitumor activities, compounds IIa-l could inhibit tumor cells PC3, Bcap37 and BGC823. These compounds displayed low to high activity by MTT assays. Among them, L-IIk, D-IIa and D-IIe were identified as potent inhibitors, with IC50 values ranging from 4.7 to 11.2 μM according to in vitro assay.
- Liu, Jing-Zi,Song, Bao-An,Fan, Hui-Tao,Bhadury, Pinaki S.,Wan, Wen-Ting,Yang, Song,Xu, Weiming,Wu, Jian,Jin, Lin-Hong,Wei, Xue,Hu, De-Yu,Zeng, Song
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scheme or table
p. 5108 - 5112
(2011/01/04)
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- Synthesis and antiviral bioactivity of chiral thioureas containing leucine and phosphonate moieties
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A series of novel chiral thioureas 3a-n bearing leucine and phosphonate moieties were synthesized in excellent yields. The structures of the compounds were completely characterized by elemental analysis, IR, 1H-, 13C-, 31P- and 19F-NMR spectral data. A half-leaf method was used to determine the in vivo protective and curative efficacies of the title products against tobacco mosaic virus (V). The compounds 3l and 3n displayed good in vivo protection and curative effects against V with inhibitory rates of 60.1, 62.8% (protection) and 56.7, 53.6% (curative) at 0.5 mg/mL, respectively. To the best of our knowledge, this is the first report on the antiviral activity of chiral thioureas containing leucine and phosphonate moieties.
- Liu, Jingzi,Yang, Song,Li, Xiangyang,Fan, Huitao,Bhadury, Pinaki,Xu, Weiming,Wu, Jian,Wang, Zhencao
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scheme or table
p. 5112 - 5123
(2011/01/04)
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- Synthesis and antiviral bioactivities of 2-cyano-3-substitutedamino(phenyl) methylphosphonylacrylates (Acrylamides) containing alkoxyethyl moieties
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An efficient reaction under microwave irradiation has been developed for the synthesis of a series of novel 2-cyano-3-substituted-amino(phenyl) methylphosphonylacrylates (acrylamides) II. The products obtained in shorter reaction time with moderate yields are fully characterized by elemental analysis, IR, 1H, 13C, and 31P NMR spectral data. The role of introducing various substituents and the effect of incorporating a-aminophosphonates with an alkoxyethyl moiety into the parent cyanoacrylate (acrylamide) structure are investigated. Among the studied compounds, both II-17 and II-24 displayed good in vivo curative, protection, and inactivation effects, which were comparable to those of the commercial reference ningnanmycin (inhibitory rates of 58.8, 60.2, 78.9% and 60.0, 58.9, 85.5%, respectively, at 500 mg/L against TMV). To the best of the authors' knowledge, this is the first report on the synthesis and antiviral activity of the title compounds II.
- Yang, Jia-Qiang,Song, Bao-An,Bhadury, Pinaki S.,Chen, Zhuo,Yang, Song,Xue-Jian, Cai,Hu, De-Yu,Xue, Wei
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experimental part
p. 2730 - 2735
(2011/07/31)
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- Reaction of 1-amino bisphosphinic acids with acid chlorides: Synthesis of novel cyclic 1-Hydroxy-1-amino-1,1-bisphosphinic acids
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Treatment of 1-amino bisphosphinic acids with HMDS followed by reaction with acid chlorides gives 1′-hydroxy-1′-amino-1,1-bisphosphinic acid in good yields. The reaction gave a mixture of the racemate and meso form of 1′-hydroxy-1′-amino-1,1-bisphosphinic acid. The stereochemistry of the readily separable diastereomer was confirmed after converting to the corresponding novel cyclic 1-hydroxy-1-amino-1,1-bisphosphinic acid. Georg Thieme Verlag Stuttgart.
- Kaboudin, Babak,Saadati, Fariba,Yokomatsu, Tsutomu
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experimental part
p. 1837 - 1840
(2010/10/02)
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- Homolytic reactions of N-bromohexamethyldisilazane with trialkyl(phenylalkoxy) derivatives of silicon and tin
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The main product of the photoinduced reaction of N- bromohexamethyldisilazane with trialkyl-(benzyloxy)derivatives of silicon and tin R3MO(CH2)nPh (R = Me, Et; M = Si, Sn; n = 1) is N,N-dibenzylidene-C-phenylmethanediamine (hydrobenzamide). For M = Si, with increase of the length of the methylene chain between the oxygen atom and the phenyl group (n = 2, 3), the similar reaction affords the product of bromination of the benzylic carbon atom R3MO(CH2) n-1CHBrPh. For M = Sn, the reaction results in the formation of 2-phenyloxacycloalkanes PhCHO(CH2)n-1. Pleiades Publishing, Ltd., 2010.
- Rakhlin,Podgorbunskaya,Voronkov
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experimental part
p. 930 - 935
(2011/01/09)
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- Cycloaddition reactions of 1,3-diazabuta-1,3-dienes with alkynyl ketenes
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The cycloaddition reactions of 'all-carbon' 1,3-diazabuta-1,3-dienes with a few conjugated and unconjugated alkynyl ketenes are described. The reactions provide some interesting azetidinones and dihydropyrimidinones bearing an alkynyl moiety. The regiochemistry of cycloadduct is related with the degree of conjugation of the alkynyl ketene. Moreover, two alternative approaches to 'all-carbon' 1,3-diazabuta-1,3-dienes are reported.
- Abbiati, Giorgio,Contini, Alessandro,Nava, Donatella,Rossi, Elisabetta
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experimental part
p. 4664 - 4670
(2009/10/09)
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- Studies on the reaction of diimines with thiourea: Synthesis and solvent-induced cis/trans-isomerization of 1,3,5-triazinane-2-thiones
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The reaction of N,Nc-bis(arylmethylidene)arylmethane diimines with thiourea under reflux in methanol was studied. The reaction gave a diastereomeric mixture of 4,6-disubstituted 1,3,5-triazinane-2-thiones in good yields. Two diastereoisomers of 4,6-diphenyl-1,3,5-triazinane-2-thione were detected in a solution of CDCl3 by NMR analysis. According to the NMR studies, the cisdiastereoisomer undergoes a solvent-induced cis/trans-isomerization process, producing the trans-diastereoisomer in DMSO. The stereochemistry of the trans-diastereoisomer was determined by Xray crystallographic analysis.
- Kaboudin, Babak,Ghasemi, Tahereh,Yokomatsu, Tsutomu
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experimental part
p. 3089 - 3093
(2009/12/28)
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- Synthesis and antiviral activities of chiral thiourea derivatives containing an α-aminophosphonate moiety
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Starting from benzaldehyde 1, the title compounds 8 were synthesized in six steps. Benzaldehyde1 was reacted with ammonium hydroxide, and the resulting imine was then treated with dialkyl phosphite 3 to give dialkyl N-(arylmethylene)-1-amino-1-aryl methylphosphonates 4. Phosphonates 4 were then easily hydrolyzed to give dialkyl 1-amino-1-aryl-methylphosphonates 6, which on treatment with triethylamine, carbon disulfide, and phosphorus oxychloride provided 7. Target compounds 8 were then prepared by the reaction of 7 with substituted chiral amine. The structures were clearly verified by spectroscopic data (IR, 1H, 13C, and 31P NMR, and elemental analysis). The bioassay of these compounds revealed them as antivirally active. It was found that title compounds 8g, 8e, 8k, and 8m had the same curative effects of TMV (inhibitory rate = 54.8, 50.5, 50.4, and 50.4%, respectively) as the commercial product Ningnanmycin (56.2%). This would appear to be the first report of the synthesis and antiviral activity of chiral thiourea derivatives containing an α-aminophosphonate moiety.
- Chen, Mei-Hang,Chen, Zhuo,Song, Bao-An,Bhadury, Pinaki S.,Yang, Song,Cai, Xue-Jian,Hu, De-Yu,Xue, Wei,Zeng, Song
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scheme or table
p. 1383 - 1388
(2010/05/18)
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- A simple, novel and convenient method for the synthesis of 1-aminophosphinic acids: synthesis of a novel C2-symmetric phosphinic acid pseudodipeptide
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A simple, efficient and novel method has been developed for the synthesis of 1-aminophosphinic acids from simple starting materials. Treatment of aromatic aldehydes with ammonia and hypophosphorus acid gives novel C2-symmetric 1-aminoarylmethylphosphinic acids. The synthesis of novel C2-symmetric phosphinic acid pseudodipeptides is also discussed.
- Kaboudin, Babak,Saadati, Fariba
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experimental part
p. 1450 - 1452
(2009/05/31)
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- Synthesis and antiviral activities of amide derivatives containing the &α-aminophosphonate moiety
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Starting from (substituted-)benzaldehydes, the title compounds 6 were synthesized through five step reactions. Benzaldehydes were treated with ammonium hydroxide, followed by dialkyl phosphite, to give dialkyl N-(arylmethylene)-1-amino-1-aryl methylphosphonates (3). Phosphonates 3 were then easily hydrolyzed to give dialkyl 1-amino-1-aryl-methylphosphonates 5. Target compounds 6 were then obtained by the reaction of 5 and substituted benzoic or cinnamic acid. Their structures were clearly verified by spectroscopic data (IR, 1H, 13C, and 31P NMR, and elemental analysis). These compounds were shown to be antivirally active in the bioassay. It was found that title compounds 6g, 6l, and 6n had the same inactivation effect of TMV (EC50 = 54.8, 60.0, and 65.2 μg/mL, respectively) as commercial product Ningnanmycin (EC50 = 55.6 μg/mL). To the best of our knowledge, this is the first report on the synthesis and antiviral activity of amide derivatives containing an α-aminophosphonate moiety.
- Hu, De-Yu,Wan, Qiong-Qiong,Yang, Song,Song, Bao-An,Bhadury, Pinaki S.,Jin, Lin-Hong,Yan, Kai,Liu, Fang,Chen, Zhuo,Xue, Wei
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supporting information; experimental part
p. 998 - 1001
(2009/05/07)
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- Synthesis and antiviral activities of cyanoacrylate derivatives containing an α-aminophosphonate moiety
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Target compounds 8 were obtained by the reaction of alkyl 2-cyano-3,3-dimethylthioacrylate or cyarylamide (7a-7e) and α- aminobenzylphosphonate (5a-5e) under reflux condition using ethanol as solvent. Their structures were clearly verified by spectroscopic data (IR and 1H, 13C, and 31P NMR) and elemental analysis. These compounds were shown to be antivirally active in the bioassay. It was found that title compounds 8d and 8e had the same inactivation effect against tobacco mosaic virus (EC50 = 55.5 and 55.3 μg/mL) as the commercial product ningnanmycin (EC50 = 50.9 μg/mL). To the best of our knowledge, this is the first report on the synthesis and antiviral activity of cyanoacrylate derivatives containing an α-aminophosphonate moiety.
- Long, Ning,Cai, Xue-Jian,Song, Bao-An,Yang, Song,Chen, Zhuo,Bhadury, Pinaki S.,Hu, De-Yu,Jin, Lin-Hong,Xue, Wei
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scheme or table
p. 5242 - 5246
(2010/04/06)
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- A novel method for the synthesis of bis(1-diethoxyphosphorylalkyl)amines from diimines
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A novel and convenient method for the synthesis of bis(1- diethoxyphosphorylalkyl)amines has been developed. As described below, treatment of aromatic diimines with diethyl phosphite in the presence of chlorotrimethylsilane gave bis(1-diethoxyphosphorylalkyl)amines. This method is easy, rapid, and good-yielding for the synthesis of bis(1- diethoxyphosphorylalkyl)amines from simple starting materials. Georg Thieme Verlag Stuttgart.
- Kaboudin, Babak,Jafari, Ehsan
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p. 3063 - 3066
(2008/02/08)
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- A mild and highly efficient protocol for the one-pot synthesis of primary α-amino phosphonates under solvent-free conditions
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Under solvent-free reaction conditions and in the presence of solid LiClO4 a novel and mild protocol for the one-pot, three-component synthesis of primary α-amino phosphonates from an aldehyde, hexamethyldisilazane and a trialkyl phosphite is described giving high yields and having short reaction times. The same products are obtained in very low yields, when the three-component reaction is carried out under microwave irradiation and in the absence of solid LiClO4. Examples of some prepared 1-aryl-N,N′-bis(arylidene)methanediamines are also described.
- Azizi, Najmedin,Rajabi, Fatemeh,Saidi, Mohammad R.
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p. 9233 - 9236
(2007/10/03)
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- Synthesis of N,N-di(arylmethylidene)arylmethanediamines by flash vacuum pyrolysis of arylmethylazides
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Flash vacuum pyrolysis of arylmethylazides 7a-d gave 2,4-diazapentadienes 5a-d in high yield (76-92%). The thermal cyclization of 5a-d gave cis-imidazolines 1a-d, further heating or Swern oxidation of 1a-d gave dehydrogenated products, imidazoles 2a-d.
- Chou, Chin-Hsing,Chu, Li-Tse,Chiu, Shao-Jung,Lee, Chin-Fan,She, Yao-Teng
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p. 6581 - 6584
(2007/10/03)
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- Microwave-assisted rapid and selective synthesis of cis- and trans-2,4,5-triarylimidazolines from aromatic aldehydes
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Microwave irradiation of a mixture of aromatic aldehydes and hexamethyldisilazane in the presence of a solid catalyst such as alumina afforded methanediamines which were efficiently converted to either cis- or trans-2,4,5-triarylimidazolines depending on the base used. A one-pot selective synthesis of cis- and transimidazolines from aromatic aldehydes was achieved under microwave irradiation.
- Uchida, Hitoshi,Tanikoshi, Hirofumi,Nakamura, Shuichi,Reddy, Paidi Yella,Toru, Takeshi
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p. 1117 - 1120
(2007/10/03)
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- Solvent-free efficient synthesis of 2,4,5-triarylimidazolines from aromatic aldehydes and hexamethyldisilazane
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A one-step preparation of 2,4,5-triarylimidazolines from aromatic aldehydes was accomplished by heating with hexamethyldisilazane under solvent-free conditions. This reaction provides a convenient preparative method for triarylimidazolines having a variety of aryl groups.
- Uchida, Hitoshi,Shimizu, Takashi,Reddy, Paidi Yella,Nakamura, Shuichi,Toru, Takeshi
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p. 1236 - 1240
(2007/10/03)
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- Regioselective synthesis of cis- and trans-2,4,5-triarylimidazolines and 2,4,5-triarylimidazoles from available reagents
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Novel data were obtained concerning the reaction of aromatic aldehydes with ammonia. A preparative method for the synthesis of new substituted 1,3,5-triaryl-2,4-diazapenta-1,4-dienes was developed. These products are the starting reactants for syntheses of cis- and trans-2,4,5-triaryl-2-imidazolines and 2,4,5-triarylimidazoles.
- Lozinskaya,Tsybezova,Proskurnina,Zefirov
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p. 674 - 678
(2007/10/03)
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- Hexamethyldisilazane as an amination agent: One-pot synthesis of isoamarine and its pyridine analogue
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The ability of hexamethyldisilazane to convert aldehydes into Schiff bases was adapted to the one-pot syntheses of isoamarine and its pyridine analogue.
- Mistryukov
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- The reductive amination of benzaldehyde over Pd/C catalysts: Mechanism and effect of carbon modifications on the selectivity
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The effects of the acidity of the carbon surface on the reactivity and selectivity of carbon supported noble metal catalysts in the amination of benzaldehyde with ammonia was studied. The equilibiria involved in the homogeneous solution were studied with 1H NMR. At the start of the reductive amination, dibenzylimine is rapidly formed, which is subsequently hydrogenated to give dibenzylamine. Benzylamine is formed by disproportionation of dibenzylimine to benzylamine and benzylimine. An increase in the number of acidic sites on the carbon support results in higher reaction rates. This may be ascribed to an acid catalysis in the establishment of relevant homogeneous equilibria and/or reduction of the concentration of the inhibiting gem-diamine intermediate at the catalyst surface. A fully selective synthesis of dibenzylamine is achieved by hydrogenation of the intermediate dibenzylimine.
- Heinen, Annemieke W.,Peters, Joop A.,Van Bekkum, Herman
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p. 2501 - 2506
(2007/10/03)
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- Synthesis of N1-unsubstituted β-lactams via a facile deprotection of N1-[(α-thiophenyl)benzyl] group
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A diastereoselective synthesis of (±) c/s-β-1actams (5 and 6) via cycloaddition reactions of N1-(α-thiophenyl)benzyl imines (3) with acid chlorides (4) in the presence of triethylamine is described. The deprotection of N1-(α-thiophenyl)benzyl group has been achieved by oxidation using potassium persulfate to give N-unsubstituted β-lactams (7) in good yields.
- Karupaiyan,Srirajan,Deshmukh,Bhawal
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p. 4375 - 4386
(2007/10/03)
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- Synthesis of N1-unsubstituted (β-lactams : Introducing n1-(1'-thiophenyl)benzyl as an N-protecting group
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A diastereoselective synthesis of (±) cis-β-lactams (5 and 6) via cycloaddition reaction of N1-(α-thiophenyl)benzyl imines (3) with acid chlorides (4) in the presence of triethyl amine is described. Deprotection of N1-(α-thiophenyl)benzyl group was achieved in good yields by oxidation using potassium persulfate.
- Karupaiyan,Srirajan,Deshmukh,Bhawal
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p. 4281 - 4284
(2007/10/03)
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- A simplified synthesis of (±)-1,2-Diphenyl-1,2-diaminoethane (1) from benzaldehyde and ammonia. Revision of the structures of the long-known intermediates 'hydrobenzamide' and 'amarine'
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A new pathway for the simple, stereocontrolled and economical synthesis of (±)-1 from benzaldehyde is described. The structures of two intermediates (Scheme 1) have been revised to those shown in Scheme 2.
- Corey,Kuehnle, Florian N. M.
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p. 8631 - 8634
(2007/10/03)
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