- Synthesis of biaryl ketones by arylation of Weinreb amides with functionalized Grignard reagents under thermodynamic controlvs.kinetic control ofN,N-Boc2-amides
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A highly efficient method for chemoselective synthesis of biaryl ketones by arylation of Weinreb amides (N-methoxy-N-methylamides) with functionalized Grignard reagents is reported. This protocol offers rapid entry to functionalized biaryl ketones after Mg/halide exchange with i-PrMgCl·LiCl under operationally-simple and practical reaction conditions. The scope of the method is highlighted in >40 examples, including bioactive compounds and pharmaceutical derivatives. Collectively, this transition-metal-free approach offers a major advantage over the recently established cross-coupling of amides by oxidative addition of N-C(O) bonds. Considering the utility of amide acylation reactions in modern synthesis, we expect that this method will be of broad interest.
- Li, Guangchen,Szostak, Michal
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supporting information
p. 3827 - 3831
(2020/06/03)
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- Kinetically Controlled, Highly Chemoselective Acylation of Functionalized Grignard Reagents with Amides by N?C Cleavage
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The direct transition-metal-free acylation of amides with functionalized Grignard reagents by highly chemoselective N?C cleavage under kinetic control has been accomplished. The method offers rapid and convergent access to functionalized biaryl ketones through transient tetrahedral intermediates. The direct access to functionalized Grignard reagents by in situ halogen–magnesium exchange promoted by the versatile turbo-Grignard reagent (iPrMgCl?LiCl) permits excellent substrate scope with respect to both the amide and Grignard coupling partners. These reactions enable facile, operationally simple and chemoselective access to tetrahedral intermediates from amides under significantly milder conditions than chelation-controlled intermediates. This novel direct two-component coupling sets the stage for using amides as acylating reagents in an alternative paradigm to the metal-chelated approach, acyl metals and Weinreb amides.
- Li, Guangchen,Szostak, Michal
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supporting information
p. 611 - 615
(2020/01/02)
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- COMPOUND FOR ORGANIC SYNTHETIC REACTION
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PROBLEM TO BE SOLVED: To provide a compound for organic synthetic reaction capable of reducing unnecessary reaction byproduct and generating a targeted chemical reaction effectively, even when a base compound sensitive to basicity is used. SOLUTION: There is provided a compound for organic synthetic reaction which is used for a coupling reaction or an addition reaction forming a bond between carbon-carbon, and is a compound represented by the structure formula (1) or a salt thereof. In the formula, (A) represents an oxygen atom or a nitrogen atom, R1 represents a substituent containing one or more carbon atom, R2 represents a substituent containing one or more carbon atom, hydrogen or halogen, and R1 and R2 may be the same or different each other. SELECTED DRAWING: Figure 2 COPYRIGHT: (C)2019,JPOandINPIT
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Paragraph 0056; 0057; 0073
(2019/05/01)
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- Rapidly Activating Pd-Precatalyst for Suzuki-Miyaura and Buchwald-Hartwig Couplings of Aryl Esters
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Esters are valuable electrophiles for cross-coupling due to their ubiquity and ease of synthesis. However, harsh conditions are traditionally required for the effective cross-coupling of ester substrates. Utilizing a recently discovered precatalyst, Pd-catalyzed Suzuki-Miyaura and Buchwald-Hartwig reactions involving cleavage of the C(acyl)-O bond of aryl esters that proceed under mild conditions are reported. The Pd(II) precatalyst is highly active because it is reduced to the Pd(0) active species more rapidly than previous precatalysts.
- Dardir, Amira H.,Melvin, Patrick R.,Davis, Ryan. M.,Hazari, Nilay,Mohadjer Beromi, Megan
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supporting information
p. 469 - 477
(2018/02/19)
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- Palladium Catalyzed Carbonylative Coupling for Synthesis of Arylketones and Arylesters Using Chloroform as the Carbon Monoxide Source
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We describe a modular, palladium catalyzed synthesis of aryl(hetero)aryl benzophenones and aryl benzoates from aryl(hetero)aryl halides using CHCl3 as the carbonyl source in the presence of KOH. The reaction occurs in tandem through an initial carbonylation to generate an aroyl halide, which undergoes coupling with arylboronic acids, bornonates, and phenols. Direct carbonylative coupling of indoles at the third position has also been accomplished under slightly modified reaction conditions by in situ activation of the C-H bond. Notably, CHCl3 is a convenient and safe alternation of CO gas, provides milder reaction conditions with high functional group tolerance, and gives the products in moderate to good yields.
- Sharma, Poonam,Rohilla, Sandeep,Jain, Nidhi
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p. 1105 - 1113
(2018/06/18)
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- Ni-Catalyzed cross-coupling reactions of N-acylpyrrole-type amides with organoboron reagents
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The catalytic conversion of amides to ketones is highly desirable yet challenging in organic synthesis. We herein report the first Ni/bis-NHC-catalyzed cross-coupling of N-acylpyrrole-type amides with arylboronic esters to obtain diarylketones. This method is facilitated by a new chelating bis-NHC ligand. The reaction tolerates diverse functional groups on both arylamide and arylboronic ester partners including sensitive ester and ketone groups.
- Huang, Pei-Qiang,Chen, Hang
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supporting information
p. 12584 - 12587
(2017/11/30)
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- N-Acylsuccinimides: Efficient acylative coupling reagents in palladium-catalyzed Suzuki coupling via C–N cleavage
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An acylative Suzuki coupling of activated amides with aryl boronic acids has been reported via palladium-catalyzed C–N bond cleavage. This protocol demonstrate amides can be activated by an atom-economic and cheap succinimide, which can be efficiently utilized to synthesize broad array of diaryl ketones in moderate to good yields.
- Cui, Ming,Chen, Zeyu,Liu, Tingting,Wang, Hui,Zeng, Zhuo
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supporting information
p. 3819 - 3822
(2017/09/15)
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- The second aryl ketone compounds
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The invention provides a synthetic method for diaryl ketone compounds. The method comprises the following steps: adding ester derivatives of raw material diaryl methanol, DDQ and water into an organic solvent, carrying out stirring, then carrying out heating to 110 to 140 DEG C and carrying out reaction for 0.5 to 12 h, and subjecting obtained reaction liquid to after-treatment so as to obtain the diaryl ketone compounds, wherein the ester derivatives of the raw material diaryl methanol have a structural formula as shown in a formula (V), (VI), (VII) or (VIII), and one-to-one correspondingly obtained products have the structural formula as shown in the formula (I), (II), (III) or (IV). The synthetic method for the diaryl ketone compounds provided by the invention has the advantages of simple, convenient and safe operation, mild reaction conditions and high product selectivity.
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Paragraph 0077; 0078
(2017/08/24)
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- Ni-Catalyzed Reductive Cross-Coupling of Amides with Aryl Iodide Electrophiles via C-N Bond Activation
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A Ni-catalyzed reductive cross-coupling reaction between two electrophiles, amides and aryl iodides, has been developed. This work is the first example using amide as an electrophile to couple with another electrophile, instead of using highly basic and pyrophoric nucleophiles. Furthermore, the Ni catalyst chemoselectively inserting the C-N bond of amide triggered the reductive cross-coupling reaction, which solves the problem that the Ni catalyst preferentially inserts the more reactive C-I bond to form a self-coupling product.
- Ni, Shengyang,Zhang, Wenzhong,Mei, Haibo,Han, Jianlin,Pan, Yi
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p. 2536 - 2539
(2017/05/24)
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- Nickel-catalyzed diaryl ketone synthesis by N-C cleavage: Direct negishi cross-coupling of primary amides by site-selective N,N-Di-boc activation
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A general Negishi acylation of primary amides enabled by a combination of site-selective N,N-di-Boc activation and nickel catalysis is reported for the first time. The reaction is promoted by a bench-stable, inexpensive Ni catalyst. The reaction shows excellent functional group compatibility, affording functionalized diaryl ketones by selective N-C cleavage. Most notably, this protocol represents the first amide cross-coupling by direct metal insertion of simple and readily available primary amides. The overall strategy by N,N-di-Boc activation/metal insertion is suitable for a broad range of coupling protocols via acylmetals. Mechanistic experiments suggest high reactivity of N,N-di-Boc activated 1° amides in direct amide C-N cross-couplings.
- Shi, Shicheng,Szostak, Michal
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p. 5872 - 5875
(2016/11/29)
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- Erbium trifluoromethanesulfonate catalyzed Friedel-Crafts acylation using aromatic carboxylic acids as acylating agents under monomode-microwave irradiation
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Erbium trifluoromethanesulfonate is found to be a good catalyst for the Friedel-Crafts acylation of arenes containing electron-donating substituents using aromatic carboxylic acids as the acylating agents under microwave irradiation. An effective, rapid and waste-free method allows the preparation of a wide range of aryl ketones in good yields and in short reaction times with minimum amounts of waste.
- Tran, Phuong Hoang,Hansen, Poul Erik,Nguyen, Hai Truong,Le, Thach Ngoc
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p. 612 - 618
(2015/02/19)
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- Palladium catalyzed addition of arylboronic acid or indole to nitriles: Synthesis of aryl ketones
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Aryl ketones can be synthesized conveniently by a palladium catalyzed addition of arylboronic acid to nitriles in aqueous triflic acid. This catalytic system was extended to the addition of unprotected indoles to nitriles under a slightly modified condition to produce 3-acyl indoles in good yields.
- Das, Tuluma,Chakraborty, Amarnath,Sarkar, Amitabha
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supporting information
p. 7198 - 7202
(2015/01/09)
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- Dirhodium(II)-Catalyzed Cross-Coupling Reactions of Aryl Aldehydes with Arylboronic Acids in Water
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In this report, dirhodium(II) catalysts with axial phosphanes ligands were employed to catalyze cross-coupling reactions of aromatic aldehydes with arylboronic acids to generate ketones in neat water. The overall reaction is proposed to occur through a cascade process involving the dirhodium-catalyzed addition of boronic acids to aldehydes followed by the dehydrogenative oxidation of alcohols.
- Kuang, Yi,Wang, Yuanhua
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supporting information
p. 1163 - 1166
(2015/10/05)
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- Synthesis of diaryl ketones via a phosphine-free Fukuyama reaction
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The synthesis of unsymmetrical diaryl ketones via the Fukuyama coupling of thioesters and organozinc reagents is described. Typically, the synthesis of diaryl ketones using this methodology provides low yields. The simple complex, Pd(dba)2, was found to convert a variety of aryl thioesters to diaryl ketones in good yields. The Royal Society of Chemistry 2011.
- Kunchithapatham, Kamala,Eichman, Chad C.,Stambuli, James P.
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supporting information; experimental part
p. 12679 - 12681
(2012/01/05)
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- Solvent-free C-benzoylation and N-benzoylation reactions using
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An ecofriendly and efficient microwave-irradiated solvent-free benzoylation method was developed. The procedure for C-benzoylation used 50 mol% AlCl 3 as a Lewis acid catalyst at 130°C and was completed in 10 min. The isolated yield was between 71% and 100%. N-benzoylation was conducted in a catalyst-free environment at 130°C in 10 min. The isolated yield was between 80% and 100%. Taylor & Francis Group, LLC.
- Al-Masum, Mohammad,Wai, Maya Chen,Dunnenberger, Henry
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experimental part
p. 2888 - 2898
(2011/09/13)
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- Synthesis of arylketones by ruthenium-catalyzed cross-coupling of aldehydes with arylboronic acids
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The first ruthenium-catalyzed cross-coupling of aldehydes with arylboronic acids is reported. Various aliphatic and aromatic aldehydes are transformed to the corresponding arylketones. A total of 31 examples with moderate to excellent yields are presented, together with the results of an initial mechanistic investigation.
- Li, Hong,Xu, Yuan,Shi, Erbo,Wei, Wei,Suo, Xiangqiang,Wan, Xiaobing
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supporting information; experimental part
p. 7880 - 7882
(2011/08/06)
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- Diaryl ketone synthesis by [RuHCl(CO)(PPh3)3]- catalyzed coupling reaction of arylboronic acids with aryl aldehydes
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[RuHCl(CO)(PPh3)3] was found to be an efficient catalyst for the coupling reaction of arylboronic acids with aryl aldehydes. The reaction proceeded smoothly in the presence of K2CO3 and H2O to give diaryl ketones in good yields. Diaryl ketones were obtained from primarily formed alcohols via Rucatalyzed transfer hydrogenation reaction.
- Fukuyama, Takahide,Okamoto, Hiromi,Ryu, Ilhyong
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p. 1453 - 1455
(2013/05/22)
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- One-pot two-step oxidative cleavage of 1,2-arylalkenes to aryl ketones instead of arylaldehydes in an aqueous medium: A complementary approach to ozonolysis
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A new approach has been developed for a one-pot and selective oxidative cleavage of aryl- and 1,2-diarylalkenes leading to one-carbon shorter aryl ketones; thereby, providing a complementary approach to classical ozonolysis. The methodology was applicable to diverse aromatic and polyaromaticarylalkenes bearing electron-donating or -withdrawing groups on the aromatic ring. The protocol also provided a useful one-pot oxidative cleavage-condensation sequence, which could potentially have important applications in natural product total synthesis. A one-pot, two-step approach has been achieved for the oxidative cleavage of 1,2-disubstituted arylalkenes into the corresponding aryl ketones instead of arylaldehydes (see scheme; NIS = N-iodosuccinimide; CTAB = cetyltrimethylammonium bromide; PDC/TBHP = pyridinium dichromate/tert-butyl hydroperoxide). The methodology also led to a valuable one-pot oxidative cleavage-condensation reaction that has widespread utility in the total synthesis of natural products.
- Sharma, Naina,Sharma, Abhishek,Kumar, Rakesh,Shard, Amit,Sinha, Arun K.
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supporting information; experimental part
p. 6025 - 6032
(2011/02/23)
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- Aryl ketone synthesis via tandem orthoplatinated triarylphosphite-catalyzed addition reactions of arylboronic acids with aldehydes followed by oxidation
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Tandem orthoplatinated triaryl phosphite-catalyzed addition reactions of arylboronic acids with aldehydes followed by oxidation to yield aryl ketones is described. 3-Pentanone was identified as a suitable oxidant for the tandem aryl ketone formation reaction. By using microwave energy, aryl ketones were obtained in high yields with the catalyst loading as low as 0.01%.
- Liao, Yuan-Xi,Hu, Qiao-Sheng
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supporting information; experimental part
p. 6986 - 6989
(2010/11/17)
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- Pd(0)/C-catalyzed cross-couplings of acyl chlorides with triarylbismuths as atom-efficient sub-stoichiometric multi-coupling reagents
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Aromatic and hetero-aromatic acyl chlorides were efficiently cross-coupled with triarylbismuths as atom-efficient nucleophilic organometallic coupling reagents in sub-stoichiometric amounts using catalytic Pd(0)/C. Thus, the coupling reactions of various triarylbismuths with a variety of acyl chlorides furnished a plethora of both symmetrical/unsymmetrical aromatic and hetero-aromatic ketones in high yields.
- Rao, Maddali L.N.,Jadhav, Deepak N.,Venkatesh, Varadhachari
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experimental part
p. 4268 - 4271
(2009/10/26)
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- Atom-efficient cross-coupling reactions of triarylbismuths with acyl chlorides under Pd(0) catalysis
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The atom-efficient cross-coupling reaction of triarylbismuths with a variety of aliphatic, aromatic, and hetero-aromatic acyl chlorides was demonstrated to afford high yields of cross-coupled ketones under palladium catalysis. The corresponding cross-coupling reaction with diacid chlorides also furnished bis-coupled ketones in good yields.
- Rao, Maddali L.N.,Venkatesh, Varadhachari,Banerjee, Debasis
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p. 12917 - 12926
(2008/03/28)
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- An atom-efficient palladium-catalyzed cross-coupling reaction of triarylbismuths with acid chlorides: synthesis of diaryl and alkyl aryl ketones
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The cross-coupling reaction of triarylbismuths with acid chlorides using a catalytic amount of PdCl2/PPh3 afforded the corresponding ketones in high yields. The reactions of aromatic and aliphatic acid chlorides occurred with atom efficiency, as 3 equiv of acid chlorides coupled effectively with 1 equiv of triarylbismuths to yield 3 equiv of the corresponding diaryl and alkyl aryl ketones.
- Rao, Maddali L.N.,Venkatesh, Varadhachari,Jadhav, Deepak N.
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p. 6975 - 6978
(2007/10/03)
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- Palladium-imidazolium-catalyzed carbonylative coupling of aryl diazonium ions and aryl boronic acids
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Palladium(II) acetate and N,N-bis-(2,6-diisopropylphenyl)dihydroimidazolium chloride (2 mol%) were used to catalyze the carbonylative coupling of aryl diazonium tetrafluoroborate salts and aryl boronic acids to form aryl ketones. Optimal conditions includ
- Andrus, Merritt B.,Ma, Yudao,Zang, Yunfu,Song, Chun
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p. 9137 - 9140
(2007/10/03)
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- Electroorganic reactions. Part 56: Anodic oxidation of 2-methyl- and 2-benzylnaphthalenes: Factors influencing competing pathways
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A systematic investigation of the anodic oxidation in nucleophilic media of 2-methyl and 2-benzylnaphthalenes, substituted at the 6-position in the naphthalene nucleus and at the 4-phenyl position of the benzylic side chain, has been carried out to identify factors favouring side-chain substitution. Cyclic voltammetry confirms that 6-substitution has a profound effect on the oxidation potentials of the naphthalene nucleus and 13C chemical shifts indicate polar effects at the benzylic carbon. However, little side-chain anodic oxidation is observed under any conditions tried; the radical-cations of electron-rich substrates preferentially dimerise and a strongly electron-withdrawing substituent at the 6-position (EtOSO2) promotes nuclear substitution. In contrast, oxidation with DDQ in aqueous acetic acid gives efficient side-chain oxidation for electron rich substrates, consistent with hydride transfer, possibly intramolecularly via a charge transfer complex.
- Utley, James H.P,Rozenberg, Gregor G
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p. 5251 - 5265
(2007/10/03)
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- Quinoline and quinazoline derivatives inhibiting platelet-derived growth factor receptor autophosphorylation and pharmaceutical compositions containing the same
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The present invention relates to novel quinoline derivatives and quinazoline derivatives represented by the following formula (I): STR1 [wherein R 1 and R 2 are each independently H or C 1 -C 4 -alkyl, or R 1 and R 2 together form C 1 -C 3 -alkylene, X is O, S or CH 2, W is CH or N, and Q is a substituted aryl group or substituted heteroaryl group] and their pharmaceutically acceptable salts, having platelet-derived growth factor receptor autophosphorylation inhibitory activity, to pharmaceutical compositions containing these compounds, and to methods for the treatment of diseases associated with abnormal cell growth such as tumors.
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- Conformational Analysis of Organic Carbonyl Compounds. Part 5. p-Methoxybenzoyl Derivatives of Benzofuran, Benzothiophene, and Naphthalene
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The conformational analysis of 2- and 3-(p-methoxybenzoyl)-benzofuran and -benzothiophene and 1- and 2-(p-methoxybenzoyl)naphthalene was performed by the n.m.r. lanthanide-induced shift (LIS) method on 1H and 13C chemical shifts with Yb(fod)3 as shi
- Benassi, Rois,Folli, Ugo,Iarossi, Dario,Schenetti, Luisa,Taddei, Ferdinando
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p. 351 - 358
(2007/10/02)
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