- An Environmentally Benign, Catalyst-Free N?C Bond Cleavage/Formation of Primary, Secondary, and Tertiary Unactivated Amides
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Herein, we report an operationally simple, cheap, and catalyst-free method for the transamidation of a diverse range of unactivated amides furnishing the desired products in excellent yields. This protocol is environmentally friendly and operates under extremely mild conditions without using any promoter or additives. Significantly, this strategy has been implied in the chemoselective synthesis of a pharmaceutical molecule, paracetamol, on a gram-scale with excellent yield. We anticipate that this universally applicable strategy will be of great interest in drug discovery, biochemistry, and organic synthesis.
- Kumar, Vishal,Dhawan, Sanjeev,Girase, Pankaj Sanjay,Singh, Parvesh,Karpoormath, Rajshekhar
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p. 5627 - 5639
(2021/11/11)
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- Direct para-Selective C-H Amination of Iodobenzenes: Highly Efficient Approach for the Synthesis of Diarylamines
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Iodine(III)-mediated synthesis of 4-iodo-N-phenylaniline from iodobenzene has been achieved, and the reaction can proceed under mild conditions. A variety of functional groups were well tolerated, providing the corresponding products in moderate to good yields. The remaining iodine group provides an effective platform for converting the products into several valuable asymmetric diphenylamines. Most importantly, this reaction can be easily scaled up to the ten-gram scale, highlighting its synthetic utility. The mechanistic study revealed that the in situ generated aryl hypervalent iodine intermediate is the key factor to realize this para-selective C-H amination reaction.
- Chen, Yujie,Huang, Zhibin,Jiang, Yaqiqi,Shu, Sai,Yang, Shan,Shi, Da-Qing,Zhao, Yingsheng
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p. 8226 - 8235
(2021/06/28)
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- Catalyst-free, direct electrochemical synthesis of annulated medium-sized lactams through C-C bond cleavage
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A catalyst-free, direct electrochemical synthesis of synthetically challenging medium-sized lactams through C-C bond cleavage has been developed. In contrast to previous typical amidyl radical cyclization, this electrosynthetic approach enabled step-economical ring expansion through a unique remote amidyl migration under mild, metal- and external-oxidant-free conditions in a simple undivided cell. The strategy features unparalleled broad substrate scope with all ring sizes of (hetero)aryl-fused 8-11-membered rings and hetero atom-tethered rings, high yields, and good functional group tolerance. Our experimental and computational findings provided strong support for a SET-based reaction manifold.
- Ackermann, Lutz,Huang, Zhixing,Kuniyil, Rositha,Li, Yueheng,Ruan, Zhixiong,Xu, Zhongnan,Zhang, Chao
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supporting information
p. 1099 - 1104
(2020/03/11)
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- Selective C-F Functionalization of Unactivated Trifluoromethylarenes
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Fluorinated organic molecules are pervasive within the pharmaceutical and agrochemical industries due to the range of structural and physicochemical properties that fluorine imparts. Currently, the most abundant methods for the synthesis of the aryl-CF2 functionality have relied on the deoxyfluorination of ketones and aldehydes using expensive and poorly atom economical reagents. Here, we report a general method for the synthesis of aryl-CF2R and aryl-CF2H compounds through activation of the corresponding trifluoromethyl arene precursors. This strategy is enabled by an endergonic electron transfer event that provides access to arene radical anions that lie outside of the catalyst reduction potential. Fragmentation of these reactive intermediates delivers difluorobenzylic radicals that can be intercepted by abundant alkene feedstocks or a hydrogen atom to provide a diverse array of difluoalkylaromatics.
- Vogt, David B.,Seath, Ciaran P.,Wang, Hengbin,Jui, Nathan T.
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supporting information
p. 13203 - 13211
(2019/09/03)
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- Synthesis of acetamides from aryl amines and acetonitrile by diazotization under metal-free conditions
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An efficient and metal-free coupling reaction has been developed that affords acetamides from the corresponding aryl amines and acetonitrile. This method tolerates a wide range of functional groups and is selective toward aryl amines. Preliminary mechanistic studies were conducted.
- Duan, Pan,Guo, Yu,Kang, Huan,Li, Yi-Na,Wen, Xianghao,Xiao, Fang,Zeng, Yao-Fu,Zhang, Na-Na
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supporting information
p. 2169 - 2172
(2019/11/25)
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- Regioselective nitration of anilines with Fe(NO3)3·9H2O as a promoter and a nitro source
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An efficient Fe(NO3)3·9H2O promoted ortho-nitration reaction of aniline derivatives has been developed. This reaction may go through a nitrogen dioxide radical (NO2) intermediate, which is generated by the thermal decomposition of iron(iii) nitrate. The practicality of the present method using nontoxic and inexpensive iron reagents has been shown by the broad substrate scope and applications.
- Gao, Yang,Mao, Yuanyou,Zhang, Biwei,Zhan, Yingying,Huo, Yanping
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supporting information
p. 3881 - 3884
(2018/06/08)
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- Direct Photocatalytic Synthesis of Medium-Sized Lactams by C?C Bond Cleavage
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Reported is a novel two-step ring-expansion strategy for expeditious synthesis of all ring sizes of synthetically challenging (hetero)aryl-fused medium-sized lactams from readily available 5–8-membered cyclic ketones. This step-economic approach features a remote radical (hetero)aryl migration from C to N under visible-light conditions. Broad substrate scope, good functional-group tolerance, high efficiency, and mild reaction conditions make this procedure very attractive. In addition, this method also provides expedient access to 13–15-membered macrolactams upon an additional one-step manipulation. Mechanistic studies indicate that the reaction involves an amidyl radical and is promoted by acid.
- Wang, Na,Gu, Qiang-Shuai,Li, Zhong-Liang,Li, Zhuang,Guo, Yu-Long,Guo, Zhen,Liu, Xin-Yuan
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supporting information
p. 14225 - 14229
(2018/10/15)
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- Monoprotected l-Amino Acid (l-MPAA), Accelerated Bromination, Chlorination, and Iodination of C(sp2)?H Bonds by Iridium(III) Catalysis
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Halogenated arenes are important structural motifs commonly found in biologically active molecules and used for a variety of transformations in organic synthesis. Herein, we report the mono-protected l-amino acid (l-MPAA) accelerated iridium(III)-catalyzed halogenation of (hetero)anilides at room temperature. This reaction constitutes the first example of an iridium(III)/l-MPAA-catalyzed general halogenation of (hetero)arenes through C(sp2)?H activation. Furthermore, we demonstrate the potential utility of our method through its use in the synthesis of a quinolone derivative.
- Kathiravan, Subban,Nicholls, Ian A.
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supporting information
p. 7031 - 7036
(2017/05/29)
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- Acetanilide and bromoacetyl-lysine derivatives as activators for human histone deacetylase 8
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In the current study, seven compounds (i.e. 1–7) were found to be novel activators for the Nε-acetyl-lysine deacetylation reaction catalyzed by human histone deacetylase 8 (HDAC8). When assessed with the commercially available HDAC8 peptide substrate Fluor-de-Lys-HDAC8 that harbors the unnatural 7-amino-4-methylcoumarin (AMC) residue immediately C-terminal to the Nε-acetyl-lysine residue to be deacetylated, our compounds exhibited comparable activation potency to that of TM-2-51, the strongest HDAC8 activator reported in the current literature. However, when assessed with an AMC-less peptide substrate derived from the native HDAC8 non-histone substrate protein Zinc finger protein ZNF318, while our compounds were all found to be able to activate HDAC8 deacetylation reaction, TM-2-51 was found not to be able to. Our compounds also seemed to be largely selective for HDAC8 over other classical HDACs. Moreover, treatment with the strongest activator among our compounds (i.e. 7) was found to decrease the KM of the above AMC-less HDAC8 substrate, while nearly maintaining the kcat of the HDAC8-catalyzed deacetylation on this substrate.
- Mukhtar, Yusif M.,Huang, Yajun,Liu, Jiajia,Chen, Di,Zheng, Weiping
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supporting information
p. 2319 - 2323
(2017/05/09)
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- 2-bromo-5- fluorine three fluorine methylbenzene preparation method
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The invention discloses a method for preparing 2-bromine-5-trifluorotoluene chloride. The method comprises the following step: under an anhydrous condition and in an organic solvent, performing cracking reaction on an anhydrous compound 1 or a compound 1', thereby preparing 2-bromine-5-trifluorotoluene chloride. According to the method, the reaction of an upper amino protecting group of m-trifluoromethyl phenylamine, the bromination reaction and the reaction of removing the amino protecting group can be all performed in one same reaction kettle without transferring or storing materials. The raw materials used in the method disclosed by the invention are cheap and easy to obtain, the reaction step is short, the reaction condition is gentle, the utilization rate of bromine is high, and the positioning selectivity of bromine feeding is high, so that a final product is low in isomeride impurity, high in reaction conversion rate, high in yield, high in product purity, low in production cost is low and applicable to industrialization production. The compound 1 and compound 1' are as shown in the specification.
- -
-
Paragraph 0093-0097
(2017/04/03)
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- Fragmentation of Protonated N-(3-Aminophenyl)Benzamide and Its Derivatives in Gas Phase
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An ion of m/z 110.06036 (ion formula [C6H8NO]+; error: 0.32 mDa) was observed in the collision induced dissociation tandem mass spectrometry experiments of protonated N-(3-aminophenyl)benzamide, which is a rearrangement product ion purportedly through nitrogen-oxygen (N–O) exchange. The N–O exchange rearrangement was confirmed by the MS/MS spectrum of protonated N-(3-aminophenyl)-O18-benzamide, where the rearranged ion, [C6H8NO18]+ of m/z 112 was available because of the presence of O18. Theoretical calculations using Density Functional Theory (DFT) at B3LYP/6-31?g(d) level suggest that an ion-neutral complex containing a water molecule and a nitrilium ion was formed via a transition state (TS-1), followed by the water molecule migrating to the anilide ring, eventually leading to the formation of the rearranged ion of m/z 110. The rearrangement can be generalized to other protonated amide compounds with electron-donating groups at the meta position, such as, –OH, –CH3, –OCH3, –NH(CH3)2, –NH-Ph, and –NHCOCH3, all of which show the corresponding rearranged ions in MS/MS spectra. However, the protonated amide compounds containing electron-withdrawing groups, including –Cl, –Br, –CN, –NO2, and –CF3, at the meta position did not display this type of rearrangement during dissociation. Additionally, effects of various acyl groups on the rearrangement were investigated. It was found that the rearrangement can be enhanced by substitution on the ring of the benzoyl with electron-withdrawing groups. [Figure not available: see fulltext.]
- Zu, Chengli,Mukhopadhyay, Sukrit,Hanley, Patrick S.,Xia, Shijing,Bell, Bruce M.,Grigg, David,Gilbert, Jeffrey R.,O’Brien, John P.
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p. 917 - 926
(2016/05/02)
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- NRF2 REGULATORS
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The present invention relates to bis aryl analogs, pharmaceutical compositions containing them and their use as Nrf2 regulators.
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Page/Page column 304
(2015/07/07)
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- Synthesis of secondary amides from N-Substituted amidines by tandem oxidative rearrangement and isocyanate elimination
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In this work an efficient tandem process transforming N-substituted amidines into secondary amides has been described. The process involves N-acylurea formation by reaction of the substrate with bis(acyloxy)(phenyl)-λ3-iodane followed by isocyanate elimination. The periodinane reagents are obtained from the commercially available phenyl-iodine(III) diacetate [PhI(OAc)2, (PIDA)] by ligand exchange with carboxylic acids. The N-substituted amidine substrates are easily synthesized from readily available nitriles. The method is applicable for secondary amide synthesis, based on both aliphatic and (hetero)aromatic amines, including challenging amides consisting of sterically hindered acids and amines. Moreover, the protocol allows one to combine steric bulk with electron deficiency in the target amides (aniline based). Such compounds are difficult to synthesize efficiently based on classical condensation reactions involving carboxylic acids and amines. Overall, the synthetic protocol transforms a nitrile into a secondary amide in both aliphatic and (hetero)aromatic systems.
- Debnath, Pradip,Baeten, Mattijs,Lefvre, Nicolas,Van Daele, Stijn,Maes, Bert U. W.
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supporting information
p. 197 - 209
(2015/03/03)
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- Schmidt reaction of ketones in dme solution in a continuous-flow microreactor
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The Schmidt reaction, the treatment with hydroazoic acid in the presence of a strong acid, converts ketones to amides directly and has been broadly applied in organic synthesis. In this communication, the Schmidt reaction of ketones was carried out in DME solution in a continuous-flow microreactor and gave the amide products. The enclosed small-volume feature of the microreactor made this reaction safe, fast, and cost-effective.
- Chen, Yuesu,Liu, Binjie,Liu, Xiaofeng,Yang, Yongtai,Ling, Yun,Jia, Yu
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supporting information
p. 1589 - 1592
(2015/02/19)
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- First aromatic ring acetamidation by anodic oxidation
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Anodic oxidation of 1-(trifluoromethyl)benzene in dry acetonitrile/Bu4NBF4under constant potential conditions led to 2-(trifluoromethyl) acetanilide in 86% yield. Other experimental conditions, as the use of constant current or the c
- Barba, Fructuoso,Barba, Isidoro,Batanero, Belen
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p. 115 - 117
(2015/01/09)
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- Conversion of aromatic amino into trifluoromethyl groups through a Sandmeyer-type transformation
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A novel strategy for aromatic trifluoromethylation by converting amino into trifluoromethyl groups via a Sandmeyer-type reaction is reported. The transformation involves diazotization of the aromatic amines with tert-butyl nitrite and hydrochloric acid to form aryldiazonium chlorides, followed by trifluoromethylation with trifluoromethylsilver at low temperature. Various readily available aromatic amines are smoothly converted under mild conditions. Georg Thieme Verlag Stuttgart. New York.
- Wang, Xi,Xu, Yan,Zhou, Yujing,Zhang, Yan,Wang, Jianbo
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supporting information
p. 2143 - 2148
(2014/08/18)
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- Silver-catalysed trifluoromethylation of arenes at room temperature
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A variety of heteroarenes and electron rich arenes can be trifluoromethylated at room temperature with TMSCF3, catalytic silver and PhI(OAc)2.
- Seo, Sangwon,Taylor, John B.,Greaney, Michael F.
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supporting information
p. 6385 - 6387
(2013/08/23)
-
- Silver-mediated trifluoromethylation of aryldiazonium salts: Conversion of amino group into trifluoromethyl group
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A novel strategy for aromatic trifluoromethylation by converting aromatic amino group into CF3 group is reported herein. This method, which can be considered as trifluoromethylation variation of the classic Sandmeyer reaction, uses readily available aromatic amines as starting materials and is performed under mild conditions.
- Wang, Xi,Xu, Yan,Mo, Fanyang,Ji, Guojing,Qiu, Di,Feng, Jiajie,Ye, Yuxuan,Zhang, Songnan,Zhang, Yan,Wang, Jianbo
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supporting information
p. 10330 - 10333
(2013/08/23)
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- Thioacids mediated selective and mild N-acylation of amines
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N-Acylated amines are ubiquitous in nature. Selective N-acylation at neutral conditions remains a key area of interest. Here we are reporting the copper sulfate-mediated highly selective, mild, and rapid N-acylation of various aliphatic and aromatic amines using thioacids in methanol at neutral conditions. All N-acylated products of primary and secondary amines were isolated in good to excellent yields. This method is found to be highly selective for the amines and not sensitive to other functional groups such as phenols, alcohols, and thiols. The simple workup, high yields, and high selectivity of this reaction can be an attractive alternative to those of the existing acyl halide- and acid anhydride-mediated N-acylation reactions.
- Mali, Sachitanand M.,Bhaisare, Rupal D.,Gopi, Hosahudya N.
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p. 5550 - 5555
(2013/07/25)
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- Quantitative insights into energy contributions of intermolecular interactions in fluorine and trifluoromethyl substituted isomeric N-phenylacetamides and N-methylbenzamides
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The presence of the C-F bond in organic molecules, particularly in the context of generating different intermolecular interactions of the type C-F...F-C, C-H...F and C-F...π is of extreme significance in the realm of structural chemistry. These interactions generate different packing motifs in the formation of the crystal. It is of interest to evaluate the energetic contributions of such weak interactions to evaluate their important role in crystal packing. In this respect, a library of twelve compounds containing a strong donor and acceptor, along with the presence of a C-F bond in different electronic environments (fluorine atom connected to C(sp2) and C(sp3) carbon atom) have been synthesized and characterized using single crystal X-ray diffraction studies at low temperature. In addition, the non-fluorinated counterpart has also been synthesized. These crystal structures have been analyzed to understand the contribution of weak interactions involving organic fluorine in the crystal packing. Furthermore, the stabilizing-destabilizing roles of such interactions in terms of favourable energetics have been quantified with inputs from calculations performed using PIXEL. It is observed that most of the interactions involving fluorine are of a dispersive character, and in some cases the interaction is also coulombic in origin. These results have been compared with ab initio quantum-chemical calculations (DFT-D3/B-97D level) performed using TURBOMOLE. In addition, the lattice energies of all the compounds have been evaluated, and the total contribution partitioned into the corresponding coulombic, polarization, dispersion and exchange contributions using the CLP module. The results correlate well with thermochemical data experimentally determined for these compounds.
- Panini, Piyush,Chopra, Deepak
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p. 3711 - 3733
(2013/07/26)
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- Copper-catalyzed trifluoromethylation of aryl and vinyl boronic acids with an electrophilic trifluoromethylating reagent
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Chemical equations presented. A copper-catalyzed trifluoromethylation of aryl- and alkenylboronic acids with Tognis reagent was described. The reaction proceeded in good to excellent yields for a range of different substrates including heteroarylboronic acids and substrates with a variety of functional groups under mild reaction conditions.
- Liu, Tianfei,Shen, Qilong
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supporting information; experimental part
p. 2342 - 2345
(2011/06/25)
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- Efficient acetylation of alcohols, phenols, and amines catalyzed by melamine trisulfonic acid (MTSA)
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Melamine trisulfonic acid (MTSA) was easily prepared by the reaction of melamine with neat chlorosulfonic acid at room temperature. This reagent can be used as an efficient catalyst for the acetylation of alcohols, phenols, and amines with Ac2O under mild and completely heterogeneous reaction conditions.
- Shirini, Farhad,Zolfigol, Mohammad Ali,Aliakbar, Ali-Reza,Albadi, Jalal
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experimental part
p. 1022 - 1028
(2010/05/18)
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- DIHYDROOROTATE DEHYDROGENASE INHIBITORS
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The invention relates to compounds of formula (I) wherein R1, R2, X1, X2, Y, Ra, Rb, Q have the meanings given in claim 1. The compounds are useful e.g. in the treatment of autoimmune disorders, such as multiple sclerosis and also in the treatment of cancer disorders.
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Page/Page column 100-101
(2010/11/03)
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- Tandem optimization of target activity and elimination of mutagenic potential in a potent series of N-aryl bicyclic hydantoin-based selective androgen receptor modulators
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Pharmacokinetic studies in cynomolgus monkeys with a novel prototype selective androgen receptor modulator revealed trace amounts of an aniline fragment released through hydrolytic metabolism. This aniline fragment was determined to be mutagenic in an Ames assay. Subsequent concurrent optimization for target activity and avoidance of mutagenicity led to the identification of a pharmacologically superior clinical candidate without mutagenic potential.
- Hamann, Lawrence G.,Manfredi, Mark C.,Sun, Chongqing,Krystek Jr., Stanley R.,Huang, Yanting,Bi, Yingzhi,Augeri, David J.,Wang, Tammy,Zou, Yan,Betebenner, David. A.,Fura, Aberra,Seethala, Ramakrishna,Golla, Rajasree,Kuhns, Joyce E.,Lupisella, John A.,Darienzo, Celia J.,Custer, Laura L.,Price, Jennifer L.,Johnson, James M.,Biller, Scott A.,Zahler, Robert,Ostrowski, Jacek
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p. 1860 - 1864
(2008/02/04)
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- Aromatic borylation/amidation/oxidation: A rapid route to 5-substituted 3-amidophenols
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5-Substituted 3-amidophenols are prepared by subjecting 3-substituted halobenzenes to an Ir-catalyzed aromatic borylation, followed by a Pd-catalyzed amidation, and finally an oxidation of the boronic ester intermediate. The entire C-H activation borylation/amidation/oxidation sequence can be accomplished without isolation of any intermediate arenes. Usefully, amide partners can include lactams, carbamates, and ureas.
- Shi, Feng,Smith III, Milton R.,Maleczka Jr., Robert E.
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p. 1411 - 1414
(2007/10/03)
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- Regioselective electrophilic trifluoromethylation of substituted anilines and derivatives in superacid
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In a one pot procedure, treatment of chloro or methyl substituted acetanilides in HF/SbF5/CCl4 followed by addition of HF/pyridine yields trifluoromethyl derivatives with high regioselectivity.
- Debarge, Sébastien,Violeau, Bruno,Bendaoud, Nohair,Jouannetaud, Marie-Paule,Jacquesy, Jean-Claude
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p. 1747 - 1750
(2007/10/03)
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- Amide conformational switching induced by protonation of aromatic substituent
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(Matrix presented) Introduction of an electron-withdrawing group on the aromatic ring of N-methylacetanilide decreased the ratio of the cis conformer, and the ratio correlates well with the Hammett σ values of the substituents. These steric properties can be applied to achieve amide conformational swiching by protonation at the aromatic substituent of 4-[bis(dimethylamino)]-N-methylacetanilide or N-[p-(dimethylamino)phenyl]-N-phenylacetamide.
- Yamasaki, Ryu,Tanatani, Aya,Azumaya, Isao,Saito, Shoichi,Yamaguchi, Kentaro,Kagechika, Hiroyuki
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p. 1265 - 1267
(2007/10/03)
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- Synthesis and evaluation of inhibitors of transthyretin amyloid formation based on the non-steroidal anti-inflammatory drug, flufenamic acid
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A light scattering-based amyloid fibril formation assay was employed to evaluate potential inhibitors of transthyretin (TTR) amyloid fibril formation in vitro. Twenty nine aromatic small molecules, some with homology to flufenamic acid (a known non-steroidal anti-inflammatory drug) were tested to identify important structural features for inhibitor efficacy. The results of these experiments and earlier data suggest that likely inhibitors will have aromatic-based structures with at least two aromatic rings. The ring or fused ring system occupying the outermost TTR binding pocket needs to be substituted with an acidic functional group (e.g. a carboxylic acid) to interact with complimentary charges in the TTR binding site. The promising TTR amyloid fibril inhibitors ranked in order of efficacy are: 2>4~7>3>9>6>21 (see Structural summary of the best transthyretin amyloid fibril formation inhibitors identified in this study. The order of efficacy is: 2>4~7>3>9>6>21.). Copyright (C) 1999 Elsevier Science Ltd.
- Baures, Paul W.,Oza, Vibha B.,Peterson, Scott A.,Kelly, Jeffery W.
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p. 1339 - 1347
(2007/10/03)
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- Electrophotographic member
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Disclosed is an electrophotographic member containing as a charge transport material a fluorine-containing N,N,N',N'-tetraarylbenzidine derivative which is remarkably excellent in solubility in an organic solvent and/or a binder such as polycarbonate resin, etc., can show very excellent electrophotographic properties such as high sensitivity, low residual potential and high durability. Further, a fluorine-containing N,N,N',N'-tetraarylbenzidine derivative usable as a charge transport material, and a process for producing the same are disclosed. Furthermore, a fluorine-containing diarylamine usable for producing the fluorine-containing N,N,N',N'-tetraarylbenzidine derivative, and a process for producing the same are disclosed.
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- Trifluoromethylation of aromatic compounds with sodium trifluoromethanesulfinate under oxidative conditions
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Radical trifluoromethylation occurs without Cu(II) but cations are involved with Cu(II). Electron-rich aromatic compounds are triluforomethylated with sodium trifluoromethanesulfinate and t-butyl hydroperoxide. Monotrifluoromethylation predominates in the presence of catalytic amounts of Cu(II) triflate whereas mono- and bis-trifluoromethylated aromatics are obtained in almost equal quantities in the absence of Cu(II).
- Langlois, Bernard R.,Laurent, Eliane,Roidot, Nathalie
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p. 7525 - 7528
(2007/10/02)
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- Synthesis and Reactivity of N-Trifluoromethyl-N-nitrosotrifluoromethanesulfonamide as a New Type of Trifluoromethylating Agent
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N-Trifluoromethyl-N-nitrosotrifluoromethanesulfonamide (TNS-Tf) was synthesized in a 58 percent yield by the reaction of trifluoronitrosomethane with hydroxylamine followed by the treatment with trifluoromethanesulfonyl fluoride in the presence of a base.TNS-Tf was demonstrated to be an effective trifluoromethylating agent photochemically or thermally for aromatics, thiols, disulfides, and uridine derivatives.The insertion reaction by two trifluoromethyl groups of TNS-Tf to the sulfur-sulfur bonds was observed in the reaction with disulfides having electron-withdrawing groups, giving 2 mols of trifluoromethylthio compounds.Furthermore, TNS-Tf served as a good reagent for mild and convenient in situ generation of trifluoromethylcopper complex which converted iodoaromatics to trifluoromethyl-substituted aromatics in good yields.Similarly, N-trifluoromethyl-N-nitrosononafluoro-1-butanesulfonamide (TNS-Nf) was synthesized in a 36 percent yield.The examination of the reactivity indicated that this type of N-nitroso sulfonamides became to be sources of both perfluoroalkyl radicals contained.
- Umemoto, Teruo,Ando, Akira
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p. 447 - 452
(2007/10/02)
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- Aromatic N-substituted halo-substituted-2-pyrrolidinones and their utility as herbicides
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Monocyclic aromatic N-substituted halo-2-pyrrolidinones having the formula STR1 in which X is hydrogen, chlorine or methyl; Y is hydrogen, chlorine or bromine, Z is chlorine or bromine; R2 is alkyl or hydrogen; R is hydrogen, alkyl, acetyl, chlorine, bromine, fluorine, iodine, trifluoromethyl, nitro, cyano, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, pentafluoropropionamido, or 3-methylureido; and R1 is hydrogen, alkyl, chlorine or trifluoromethyl. The compounds of this invention are prepared by a novel process and are useful as herbicides.
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