- Ni-Catalyzed Aryl Sulfide Synthesis through an Aryl Exchange Reaction
-
A Ni-catalyzed aryl sulfide synthesis through an aryl exchange reaction between aryl sulfides and a variety of aryl electrophiles was developed. By using 2-pyridyl sulfide as a sulfide donor, this reaction achieved the synthesis of aryl sulfides without using odorous and toxic thiols. The use of a Ni/dcypt catalyst capable of cleaving and forming aryl-S bonds was important for the aryl exchange reaction between 2-pyridyl sulfides and aryl electrophiles, which include aromatic esters, arenol derivatives, and aryl halides. Mechanistic studies revealed that Ni/dcypt can simultaneously undergo oxidative additions of aryl sulfides and aromatic esters, followed by ligand exchange between the generated aryl-Ni-SR and aryl-Ni-OAr species to furnish aryl exchanged compounds.
- Isshiki, Ryota,Kurosawa, Miki B.,Muto, Kei,Yamaguchi, Junichiro
-
p. 10333 - 10340
(2021/07/21)
-
- Trialkylammonium salt degradation: Implications for methylation and cross-coupling
-
Trialkylammonium (most notably N,N,N-trimethylanilinium) salts are known to display dual reactivity through both the aryl group and the N-methyl groups. These salts have thus been widely applied in cross-coupling, aryl etherification, fluorine radiolabelling, phase-transfer catalysis, supramolecular recognition, polymer design, and (more recently) methylation. However, their application as electrophilic methylating reagents remains somewhat underexplored, and an understanding of their arylation versus methylation reactivities is lacking. This study presents a mechanistic degradation analysis of N,N,N-trimethylanilinium salts and highlights the implications for synthetic applications of this important class of salts. Kinetic degradation studies, in both solid and solution phases, have delivered insights into the physical and chemical parameters affecting anilinium salt stability. 1H NMR kinetic analysis of salt degradation has evidenced thermal degradation to methyl iodide and the parent aniline, consistent with a closed-shell SN2-centred degradative pathway, and methyl iodide being the key reactive species in applied methylation procedures. Furthermore, the effect of halide and non-nucleophilic counterions on salt degradation has been investigated, along with deuterium isotope and solvent effects. New mechanistic insights have enabled the investigation of the use of trimethylanilinium salts in O-methylation and in improved cross-coupling strategies. Finally, detailed computational studies have helped highlight limitations in the current state-of-the-art of solvation modelling of reaction in which the bulk medium undergoes experimentally observable changes over the reaction timecourse. This journal is
- Assante, Michele,Baillie, Sharon E.,Juba, Vanessa,Leach, Andrew G.,McKinney, David,Reid, Marc,Washington, Jack B.,Yan, Chunhui
-
p. 6949 - 6963
(2021/06/02)
-
- Nickel-Catalyzed Amination of Aryl Chlorides with Amides
-
A nickel-catalyzed amination of aryl chlorides with diverse amides via C-N bond cleavage has been realized under mild conditions. A broad substrate scope with excellent functional group tolerance at a low catalyst loading makes the protocol powerful for synthesizing various aromatic amines. The aryl chlorides could selectively couple to the amino fragments rather than the carbonyl moieties of amides. Our protocol complements the conventional amination of aryl chlorides and expands the usage of inactive amides.
- Li, Jinpeng,Huang, Changyu,Wen, Daheng,Zheng, Qingshu,Tu, Bo,Tu, Tao
-
supporting information
p. 687 - 691
(2021/01/09)
-
- Method for catalyzing N-alkylation of aminopyridine
-
The invention discloses a method for catalyzing N-alkylation of aminopyridine. The method comprises the step of reacting an aminopyridine compound with an alkylation raw material in the presence of a heterogeneous catalyst to obtain an N-alkylated aminopyridine compound. The alkylation reaction has high activity and selectivity, is simple to operate and low in catalyst price, does not need other reaction steps, is beneficial to large-scale industrial production, and compared with previous reports, does not need to use a large amount of noble metals, can be continuously carried out, and does not use other expensive organic raw materials or reducing agents in the process. Generation of a large amount of organic waste liquid and solid waste is avoided, and collection operation of process products is simple.
- -
-
Paragraph 0087-0091
(2021/08/07)
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- A Novel One-Pot Synthesis of N,N-Dimethylaminopyridines by Diazotization of Aminopyridines in Dimethylformamide in the Presence of Trifluoromethanesulfonic Acid
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Abstract: Diazotization of aminopyridines in the presence of trifluoromethanesulfonic acid gives the corresponding pyridinyl trifluoromethanesulfonates instead of expected diazonium salts. Pyridinyl trifluoromethanesulfonates can be converted to N,N-dimethylaminopyridines on heating in dimethylformamide via replacement of the trifluoromethanesulfonyloxy group. The reaction is accelerated under microwave irradiation. A novel one-pot procedure has been proposed for the synthesis of 2- and 4-(dimethylamino)pyridines from commercially available aminopyridines. The procedure provides high yields of the target products, and it can be regarded as an alternative to the known methods of synthesis of N,N-dimethylpyridin-4-amine (DMAP) widely used as base catalyst in organic synthesis.
- Filimonov, V. D.,Krasnokutskaya, E. A.,Potapova, M. I.,Sanzhiev, A. N.
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p. 1023 - 1028
(2020/07/25)
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- Iron-catalyzed protodehalogenation of alkyl and aryl halides using hydrosilanes
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A simple and efficient iron-catalyzed protodehalogenation of alkyl and aryl halides using phenylhydrosilane is disclosed. The reaction utilizes FeCl3 without the requirement of ligands. Unactivated alkyl and aryl halides were successfully reduced in good yields; sterically hindered tertiary halides were also reduced including the less reactive chlorides. The scalability of this methodology was demonstrated by a gram-scale synthesis with a catalyst loading as low as 0.5 mol%. Notably, disproportionation of phenylsilane leads to diphenylsilane that further reduces the halides. Preliminary mechanistic studies revealed a non-radical pathway and the source of hydrogen is PhSiH3via deuterium labeling studies. Our methodology represents simplicity and provides a good alternative to typical tin, aluminum and boron hydride reagents.
- Pilli, Ramadevi,Balakrishnan, Venkadesh,Chandrasekaran, Revathi,Rasappan, Ramesh
-
supporting information
p. 1749 - 1753
(2019/02/20)
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- Amination of Aromatic Halides and Exploration of the Reactivity Sequence of Aromatic Halides
-
A base-promoted amination of aromatic halides has been developed using a limited amount of dimethylformamide (DMF) or amine as an amino source. Various aryl halides, including F, Cl, Br, and I, have been successfully aminated in good to excellent yields. Although the amination of aromatic halides with amines or DMF is usually considered as an aromatic nucleophilic substitution (SNAr) process, and the reactivity of an aromatic halide is F > Cl > Br > I, the reactivity of aromatic halides in this system was found to be I > Br a‰ F > Cl. This protocol also showed a good regioselectivity for multihalogenated aromatics. This protocol is valuable for industrial application due to the simplicity of operation, the unrestricted availability of amino sources and aromatic halides, transition metal-free conditions, no requirement for solvent, and scalability.
- Yang, Chu,Zhang, Feng,Deng, Guo-Jun,Gong, Hang
-
p. 181 - 190
(2019/01/10)
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- Iron-Catalyzed Selective N-Methylation and N-Formylation of Amines with CO2
-
We herein describe an efficient iron-catalyzed selective N-methylation and N-formylation of amines with CO2 and silane using mono-phosphine as ligand. With commercially available [CpFe(CO)2]2 as catalyst, Fe-catalyzed methylation of amines was achieved with triphenylphosphine as a ligand. Using tributylphosphine as a ligand, Fe-catalyzed formylation of amines was realized at a lower temperature. The method was successfully applied in the late-stage methylation and formylation of drug molecules containing amine moiety. (Figure presented.).
- Li, Wen-Duo,Zhu, Dao-Yong,Li, Gang,Chen, Jie,Xia, Ji-Bao
-
supporting information
p. 5098 - 5104
(2019/11/03)
-
- UiO-type metal-organic frameworks with NHC or metal-NHC functionalities for: N-methylation using CO2 as the carbon source
-
We demonstrate the first metal-organic framework (MOF) that catalyzes N-methylation of amines using 1 atm CO2 and phenylsilane under ambient conditions. Compared with its homogeneous analog, the incorporation of N-heterocyclic carbene (NHC) into the MOF provides more efficient catalysis with improved reaction kinetics, turnover numbers and recyclability. Moreover, the metalated NHC functionalized MOF achieves direct N-methylation of amines bearing carboxylate moieties, which are common building blocks in pharmaceutical chemistry.
- Zhang, Xu,Jiang, Yilin,Fei, Honghan
-
supporting information
p. 11928 - 11931
(2019/10/11)
-
- DBU-Catalyzed Selective N-Methylation and N-Formylation of Amines with CO2 and Polymethylhydrosiloxane
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We describe herein an efficient organocatalytic system for the selective N-methylation and N-formylation of amines with carbon dioxide (CO2) as a sustainable C1 feedstock and polymethylhydrosiloxane (PMHS) as a cost-effectvie reducing reagent. High-yielding N-methylation products are obtained with low catalyst loading (1%) of DBU. Selective N-formylation of amines is achieved using the same catalytic system at a lower reaction temperature. (Figure presented.).
- Li, Gang,Chen, Jie,Zhu, Dao-Yong,Chen, Ye,Xia, Ji-Bao
-
supporting information
p. 2364 - 2369
(2018/05/07)
-
- General method for nucleophilic aromatic substitution of aryl fluorides and chlorides with dimethylamine using hydroxide-assisted decomposition of N,N-dimethylforamide
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A practical and convenient procedure for the nucleophilic aromatic substitution of aryl fluorides and chlorides with dimethylamine was developed using a hydroxide-assisted thermal decomposition of N,N-dimethylforamide. These conditions are tolerant of nitro, nitrile, aldehyde, ketone, and amide groups but will undergo acyl substitution to form amides for methyl esters and acyl chlorides. Isolated yields of the products range from 44% to 98%, with the majority being greater than 70% for 17 examples.
- Garcia, Juana,Sorrentino, Jacob,Diller, Emily J.,Chapman, Daniel,Woydziak, Zachary R.
-
supporting information
p. 475 - 481
(2016/04/05)
-
- Room-temperature copper-catalyzed arylation of dimethylamine and methylamine in neat water
-
The first room-temperature copper-catalyzed arylations of dimethylamine and methylamine in neat water have been developed. Using a combination of CuI and 6,7-dihydroquinolin-8(5 H)-one oxime as catalyst, dimethylamine is arylated with various aryl halides to give the corresponding products in good to excellent yields. Further, this catalysis enables the selective arylation of methylamine to afford the high yields of monoarylated methylamines as the sole products.
- Wang, Deping,Kuang, Daizhi,Zhang, Fuxing,Yang, Chunlin,Zhu, Xiaoming
-
supporting information
p. 714 - 718
(2015/03/18)
-
- Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids
-
A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts.
- Fu, Ming-Chen,Shang, Rui,Cheng, Wan-Min,Fu, Yao
-
supporting information
p. 9042 - 9046
(2015/08/03)
-
- General catalytic methylation of amines with formic acid under mild reaction conditions
-
A general catalytic protocol for the methylation of amines has been developed applying, for the first time, formic acid as the C1 building block and silanes as reducing agents. A broad range of aromatic and aliphatic, both primary and secondary, amines has been converted to the corresponding tertiary amines including [N-13C]-labelled drugs in good to excellent yields under mild conditions. Methylation made easy: A general catalytic protocol for the methylation of amines has been developed applying, for the first time, formic acid as the C1 building block and silanes as reducing agents. A broad range of aromatic and aliphatic, both primary and secondary, amines has been converted to the corresponding tertiary amines, including [N-13C]-labelled drugs, in good to excellent yields at mild conditions (see scheme; dppp=(1,3-bis(diphenylphosphino)propane)).
- Sorribes, Ivan,Junge, Kathrin,Beller, Matthias
-
supporting information
p. 7879 - 7883
(2014/07/07)
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- A general method for N-methylation of amines and nitro compounds with dimethylsulfoxide
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DMSO methylates a broad range of amines in the presence of formic acid, providing a novel, green and practical method for amine methylation. The protocol also allows the one-pot transformation of aromatic nitro compounds into dimethylated amines in the presence of a simple iron catalyst. Not just a solvent: DMSO methylates a broad range of amines in the presence of formic acid, providing a novel, green and practical method for amine methylation. The protocol also allows the one-pot transformation of aromatic nitro compounds into dimethylated amines in the presence of a simple iron catalyst. Copyright
- Jiang, Xue,Wang, Chao,Wei, Yawen,Xue, Dong,Liu, Zhaotie,Xiao, Jianliang
-
supporting information
p. 58 - 63
(2014/01/17)
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- A general catalytic methylation of amines using carbon dioxide
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Putting CO2 to work: Carbon dioxide is shown to be a general and selective methylating reagent for secondary and primary, aromatic and aliphatic amines under reductive conditions. A variety of tertiary amines are obtained from CO2 and commercially available silanes in high yields with good tolerance to nitrile, olefin, ether, ester, and hydroxy groups. Copyright
- Li, Yuehui,Fang, Xianjie,Junge, Kathrin,Beller, Matthias
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p. 9568 - 9571
(2013/09/23)
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- Microwave assisted suzuki-miyaura and ullmann type homocoupling reactions of 2- and 3-halopyridines using a Pd(OAc)2/benzimidazolium salt and base catalyst system
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A number of novel benzimidazole derivatives 1-4 were synthesized and the catalytic activity of these compounds in a catalytic system consisting of a benzimidazolium salt/Pd(OAc)2/K2CO3 were investigated in the Suzuki-Miyaura and Ullmann type homocoupling reactions under microwave irradiation. We obtained both cross coupling and homocoupling products of pyridine and some side products such as dimethylaminopyridine and unsubstituted pyridine.
- Yilmaz, Uelkue,Deniz, Selma,Kuecuekbay, Hasan,Sireci, Nihat
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p. 3712 - 3724
(2013/06/04)
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- NOVEL CATALYSTS
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The present invention provides novel compounds and ligands that are useful in transition metal catalyzed cross-coupling reactions. For example, the compounds and ligands of the present invention are useful in palladium or gold catalyzed cross-coupling reactions.
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-
Page/Page column 68-69
(2012/06/01)
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- A highly versatile catalyst system for the cross-coupling of aryl chlorides and Amines
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The syntheses of 2-(di-tertbutylphosphino)-N,N-dimethylaniline (L1, 71%) and 2-(di-1-adamantylphosphino)-N,N-dimethylaniline (L2, 74%), and their application in BuchwaldHartwig amination, are reported. In combination with [Pd(allyl)Cl]2 or [Pd(cinnamyl)Cl]2, these structurally simple and air-stable P,N ligands enable the cross-coupling of aryl and heteroaryl chlorides, including those bearing as substituents enolizable ketones, ethers, esters, carboxylic acids, phenols, alcohols, olefins, amides, and halogens, to a diverse range of amine and related substrates that includes primary alkyl- and arylamines, cyclic and acyclic secondary amines, N-H imines, hydrazones, lithium amide, and ammonia. In many cases, the reactions can be performed at low catalyst loadings (0.5-0.02 mol % Pd) with excellent functional group tolerance and chemoselectivity. Examples of cross-coupling reactions involving 1,4-bromochlorobenzene and iodobenzene are also reported. Under similar conditions, inferior catalytic performance was achieved when using Pd(OAc)2, PdCl2, [PdCl2(cod)] (cod = 1,5-cyclooctadiene), [PdCl 2(MeCN)2], or [Pd2(dba)3] (dba = dibenzylideneacetone) in combination with L1 or L2, or by use of [Pd(allyl)Cl]2 or [Pd(cinnamyl)Cl]2 with variants of L1 and L2 bearing less basic or less sterically demanding substituents on phosphorus or lacking an ortto-dimethylamino fragment. Given current limitations associated with established ligand classes with regard to maintaining high activity across the diverse possible range of C-N coupling applications, L1 and L2 represent unusually versatile ligand systems for the cross-coupling of aryl chlorides and amines
- Lundgren, Rylan J.,Sappong-Kumankumah, Antonia,Stradiotto, Mark
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supporting information; experimental part
p. 1983 - 1991
(2010/07/03)
-
- A mild, catalyst-free synthesis of 2-aminopyridines
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Alkylation of 2-mercaptopyridine with 1,2-dibromoethane affords a cyclic dihydrothiazolopyridinium salt that can serve as a precursor of 2-aminopyridines. Its reaction with primary or secondary amines, either neat or in DMSO, under mild conditions gives the title compounds.
- Poola, Bhaskar,Choung, Wonken,Nantz, Michael H.
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p. 10798 - 10801
(2008/12/23)
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- Direct uncatalyzed amination of 2-chloropyridine using a flow reactor
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Chloropyridines are efficiently converted into 2-amino-pyridines by uncatalyzed nucleophilic aromatic substitution (SNAr) in NMP using a continuous-flow reactor. A variety of secondary amines undergo SNAr with both electron-rich and electron-deficient 2-chloropyridines to afford 2-aminopyridines in good to excellent yield. The flow reactor, which provides a short reaction time and high temperatures up to 300°C, can overcome the activation barrier for reactions with unactivated substrates. Short reaction times result in fewer side products and can afford milligram to multigram quantities of product using continuous flow. Georg Thieme Verlag Stuttgart.
- Hamper, Bruce C.,Tesfu, Eden
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p. 2257 - 2261
(2008/02/10)
-
- ANTIBACTERIAL COMPOSITIONS
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Compounds of formula (I) have antibacterial activity: wherein: m is 0 or 1 ; Q is hydrogen or cyclopropyl; AIk is an optionally substituted, divalent C1-C6 alkylene, alkenylene or alkynylene radical which may contain an ether (-O-), thioether (-S-) or amino (-NR)- link, wherein R is hydrogen, -CN or C1-C3 alkyl; X is -C(=O)NR6-, -S(O)NR6-, -C(=O)O- or -S(=O)O- wherein R6 is hydrogen, optionally substituted C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, -Cyc, or -( C1-C3 alkyl)-Cyc wherein Cyc is optionally substituted monocyclic carbocyclic or heterocyclic having 3-7 ring atoms; Z is N or CH, or CF; R2 and R3 are as defined in the description.
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Page/Page column 68-69
(2008/06/13)
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- Method for treating multi-drug resistant tumors
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Methods for administering mitomycin C to a multi-drug resistant cell and for reducing the toxicity of the compound are described. In the methods, mitoymic C is provided in the form of a prodrug conjugate, where the drug is linked to a hydrophobic moiety, such as a lipid, through a cleavable dithiobenzyl linkage. The dithiobenzyl linkage is susceptible to cleavage by mild thiolysis, resulting in release of mitomycin C in its original form. The linkage is stable under nonreducing conditions. The prodrug conjugate can be incorporated into liposomes for administration in vivo and release of mitomycin C in response to endogenous in vivo reducing conditions or in response to administration of an exogenous reducing agent.
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- Double geminal C-H activation and reversible α-elimination in 2-aminopyridine iridium(III) complexes: The role of hydrides and solvent in flattening the free energy surface
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[H2Ir(OCMe2)2L2]BF4 (1) (L = PPh3), a preferred catalyst for tritiation of pharmaceuticals, reacts with model substrate 2-(dimethylamino)pyridine (py-NMe2; py = 2-pyridyl) to give chelate carbene [H 2Ir(py-N(Me)CH=)L2]BF4 (2a) via cyclometalation, H2 loss, and reversible α-elimination. Agostic intermediate [H2Ir(py-N(Me)CH2-H)L2]BF 4 (4a), seen by NMR, is predicted (DFT(B3PW91) computations) to give C-H oxidative addition to form the alkyl intermediate [(H)(η2- H2)Ir(py-N(Me)CH2-)L2]BF4. Loss of H2 leads to the fully characterized alkyl [HIr(OCMe 2)(py-N(Me)CH2-)L2]BF4 (3a Me2CO), which loses acetone to give alkylidene hydride 2a by rapid reversible α-elimination. 2a rapidly reacts with excess H2 in d6-acetone to generate [H2Ir(OC(CD3) 2)2L2]BF4 (1-d12), 3a(CD3)2CO, and py-NMe2 in a 1:1:1 ratio, showing reversibility and accounting for the selective isotope exchange catalyzed by 1. Reaction of 1 with py-N(CH2)4 gives the fully characterized carbene 2c. A cis-L2 carbene intermediate, cis-2c, observed by NMR, reacts with CO via retro α-elimination to give the alkyl 3cCO, while the trans isomer, 2c, does not react; retro α-elimination thus requires the Ir-H bond to be orthogonal to the carbene plane. Consistent with experiment, computational studies show a particularly flat PE surface with activation of the agostic C-H bond giving a less stable H2 complex, then formation of a kinetic carbene complex with cis-L, only seen experimentally for py-N(CH2)4. Hydrides at key positions, together with gain or loss of solvent and H2, flatten the PE (AG) surfaces to allow fast catalysis.
- Clot, Eric,Chen, Junyi,Lee, Dong-Heon,Sung, So Young,Appelhans, Leah N.,Faller, Jack W.,Crabtree, Robert H.,Eisenstein, Odile
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p. 8795 - 8804
(2007/10/03)
-
- Synthesis of aminopyridines via an unprecedented nucleophilic aromatic substitution of cyanopyridines
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The direct reaction of 2- and 4-cyanopyridines with lithium amides affords good yields of the corresponding aminopyridines via displacement of cyanide. Addition of CsF accelerates the reaction and can lead to significantly higher yields.
- Penney, Jonathan M.
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p. 2667 - 2669
(2007/10/03)
-
- Design of 2,5-dimethyl-3-(6-dimethyl-4-methylpyridin-3-yl)-7-dipropylamino- pyrazolo[1,5-a]pyrimidine (NBI 30775/R121919) and structure-activity relationships of a series of potent and orally active corticotropin-releasing factor receptor antagonists
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We previously shown that 3-phenylpyrazolo[1,5-a]pyrimidines exemplified by 8 were potent antagonists of the human corticotropin-releasing factor-1 receptor. A series of 3-pyridylpyrazolo-[1,5-a]pyrimidines 15, 25-30, 34, and 35 containing a weakly basic pyridine ring at the 3-position of the bicyclic nucleus was designed to reduce lipophilicity from the initial leads such as 7. Here, we showed that these 3-pyridyl compounds exhibited potent antagonists at the human CRF1 receptor. Moreover, the hydrophilic and weakly basic pyridine moiety increased the water solubility of some analogues. Compound 26h exhibited good binding affinity at the human CRF1 receptor with a Ki value of 3.5 nM. As a functional antagonist, it dose-dependently inhibited CRF-stimulated cAMP production in cells expressing the CRF1 receptor (IC50 = 50 nM), and CRF-stimulated ACTH release from cultured rat pituitary cells (IC50 = 20 nM). 26h had a log P value of 4.9 and water solubility of greater than 10 mg/mL. Pharmacokinetic studies in rats showed that 26h was orally bioavailable and able to penetrate into the brain. 26h has been demonstrated in vivo efficacy in animal behavioral models that measure anxiolytic activity. These results suggest that analogues from this series were potent CRF1 receptor antagonists with proper physicochemical properties and good pharmacokinetic profiles. 26h was developed into a clinical compound and exhibited efficacy in patients with major depression.
- Chen, Chen,Wilcoxen, Keith M.,Huang, Charles Q.,Xie, Yun-Feng,McCarthy, James R.,Webb, Thomas R.,Zhu, Yun-Fei,Saunders, John,Liu, Xin-Jun,Chen, Ta-Kung,Bozigian, Haig,Grigoriadis, Dimitri E.
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p. 4787 - 4798
(2007/10/03)
-
- Aminoborohydrides 15. The First Mild and Efficient Method for Generating 2-(Dialkylamino)-pyridines from 2-Fluoropyridine
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(Matrix presented) Lithium aminoborohydride (LAB) reagents promote the amination of 2-fluoropyridine under mild reaction conditions, providing 2-(dialkylamino)-pyridines in excellent yield and purity. Treatment of 2-fluoropyridine with 1.1 equiv of lithiu
- Thomas, Shannon,Roberts, Sara,Pasumansky, Lubov,Gamsey, Soya,Singaram, Bakthan
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p. 3867 - 3870
(2007/10/03)
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- Triaromatic vitamin D analogues
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The invention relates, as novel and useful industrial products, to triaromatic compounds, which are vitamin D analogues, of general formula (I): and also to a method for preparing them and to their use in pharmaceutical compositions intended for use in human or veterinary medicine, or alternatively in cosmetic compositions.
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- Cryptophycin compound
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The present invention provides antitumor methods, formulations, and compounds comprising a cryptophycin.
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-
- Oxidation catalyst and oxidation process using the same
-
In the presence of (1) an oxidation catalyst comprising a crystalline complex of manganese with an N,N′-disalicylidenediamine (e.g., N,N′-disalicylidene C2-8alkylenediamines and N,N′-disalicylidene C6-12arylenediamines), or (2) an oxidation catalyst comprising the above complex and a basic nitrogen-containing compound, a substrate (e.g., β-isophorone or a derivative thereof) is oxidized with molecular oxygen to produce a corresponding oxide (e.g., ketoisophorone). Ketoisophorone can be obtained from β-isophorone with high conversion and high selectivity.
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- Oxidation catalytic system and process for producing ketoisophorone using the same
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In the presence of a catalytic system comprising a cyclic base and a complex of a transition metal with an N,N'-disalicylidenediamine, ketoisophorone or a derivative thereof is produced by oxidizing beta -isophorone or a derivative thereof with molecular oxygen with controlling the water content of a reaction system to 1% by weight or less at the initial stage of the reaction. Moreover, the above catalytic system further comprises a basic nitrogen-containing compound. The complex may be an N,N'-disalicylidene C2-5 alkylenediamine complex with manganese, iron, cobalt, copper, or vanadium. The cyclic base may be an alicyclic or aromtaic compound having at least two nitrogen atoms. As the basic nitrogen-containing compound, a Schiff base such as an imino compound and an anil compound can be used. The proportion of the nitrogen-containing compound to the complex is about 0.1/1 to 20/1 (molar ratio). With the above oxydation catalytic system, there can be obtained ketoisophorone and derivatives thereof with high efficiency.
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-
- N-Heteroarylphosphonates, Part II. Synthesis and reactions of 2- and 4- phosphonatoquinolines and related compounds
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We extend our synthetic method for the efficient preparation of dialkoxyphosphoryl- and phosphonio-disubstituted pyridines to include the preparation of other phosphonato substituted N-heterocycles. The key to the success of this method lies in the employment of cationic N- (trifluoromethylsulfonyl)heteroarylium triflates that are activated towards nucleophilic attack. The P(O)(OR)2 group can be transformed into the P(S)(OR)2 functionality. We report first attempts to substitute the P(O)(OR)2 moiety with C-nucleophiles. In addition to our synthetic results, the X-ray structures of two (dimethoxyphosphoryl)trifluoromethanesulfonyldihydro-N-heteroarenes are discussed. We also give complete carbon (13C) and phosphorus (31P)-NMR spectra of a series of 2- and 4-phosphonic ester substituted heteroaryl compounds and their dihydro analogs.
- Haase, Mirko,Guì?nther, Wolfgang,Goì?rls, Helmar,Anders, Ernst
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p. 2071 - 2081
(2007/10/03)
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- A very convenient dimethylamination of activated aromatic halides using N,N-dimethylformamide and ethanolamines
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A very convenient dimethylamination of activated aromatic halides was achieved by using N,N-dimethylformamide(DMF) and ethanolamines. p- Nitrochlorobenzene, 2-halopyridines, 2-chloroquinoline and 2-chloropyrimidine gave the corresponding dimethylamino substituted products when treated with DMF and diethanolamine in 80-92% yield.
- Cho, Yoon Hwan,Park, Jae Chan
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p. 8331 - 8334
(2007/10/03)
-
- Reaction of Pyridine and Picolines N-oxides with Hexamethylphosphoroamide. New Way to Dimethylamino Derivatives of Azaaromatic Compounds
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The reaction of pyridine, 2-, 3-, and 4-picoline N-oxides with hexamethylphosphoramide (HMPA) was studied in the temperature range of 150-230 deg C with and without polyphosphoric acid (PPA) as catalyst. Pyridine and 3-picoline N-oxides gave their 2-dimethylamino derivatives as well as deoxygenation products. In the case of 2- and 4-picoline N-oxides 2- and 4-dimethylaminomethylpyridines were formed, respectively as well as 2- and 4-picoline. Key words: hexamethylphosphoramide, pyridine and picoline N-oxides, 2-dimethylaminopyridine, 2- and 4- dimethylaminomethylpyridines
- Czuba, W.,Wodzinska, J.
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p. 1343 - 1346
(2007/10/02)
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- 4'-substituted nucleosides
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Nucleosides compounds of Formula I: STR1 wherein B is a purine or a pyrimidine; X and X' are H; Y is H; Y' is OH, F or H; or Y' and X' together makes a bond; Z is STR2 where n is zero, one, two or three; or Y' and Z together form a cyclic phosphate ester; Z' is --CN, --CH3, CH2 N3 or --CH2 J, where J is a halogen atom; or Z' and Y' together are --CH2 O--; and pharmaceutically acceptable esters, ethers, amides, N-acyl moieties and salts thereof.
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- Microbicides
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Compounds of the formula STR1 in which R1 is hydrogen, halogen, methyl, methoxy or trifluoromethyl; n is 1 or 2; R2 is hydrogen, C1 -C6 alkyl, C1 -C3 alkyl which is substituted by halogen, cyano or methoxy, or is C2 -C5 alkenyl, C2 -C5 alkynyl, benzyl, COR5, CON(R5)R6, CSN(R5)R6, CO(OR6), CO(SR6), CS(SR5), SO2 R7, PO(OR6)2 or Si(R6)3 ; R3 and R4 independently of one another are hydrogen, C1 -C5 alkyl, CH2 OR6, cyclopropyl, methylcyclopropyl, C2 -C5 alkenyl, C2 -C5 alkynyl or C1 -C2 haloalkyl; R5 is hydrogen, C1 -C6 alkyl, C1 -C3 alkyl which is substituted by 1 to 3 halogens, C1 -C3 alkyl which is substituted or OR6 or SR6, or is C2 -C5 alkenyl, C2 -C5 alkenyl which is substituted by 1 to 3 halogens, C2 -C5 alkynyl, C3 -C6 cycloalkyl, phenyl or phenyl which is monosubstituted to trisubstituted by halogen, C1 -C3 alkyl, C1 -C3 haloalkyl, C1 -C3 alkoxy, nitro or cyano; R6 is C1 -C6 alkyl; R7 is C1 -C3 alkyl, phenyl, phenyl which is monosubstituted or disubstituted by halogen, C1 -C2 alkyl, C1 -C2 haloalkyl, methoxy or nitro; including the acid addition salts, have valuable microbicidal properties. The novel active substances can be employed in crop protection for preventing crop plants being attacked by phytopathogenic microorganisms, and for controlling these pests.
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- Method for making aromatic ethers using diorganoamino pyridinum salt catalyst
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A method is provided for making aromatic ethers by effecting the displacement of reactive radicals on an activated aromatic nucleus such as a phthalimide with a mono or bisalkali metal phenoxide in the presence of an organic solvent and a dialkylamino branched alkyl substituted pyridinium salt as a phase transfer catalyst. Improved yields of bis(aromatic ethers) are achieved without the production of undesirable by-products, such as alkylated phenols.
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