- Silylcarboxylic Acids as Bifunctional Reagents: Application in Palladium-Catalyzed External-CO-Free Carbonylative Cross-Coupling Reactions
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A palladium-catalyzed external-CO-free carbonylative Hiyama-Denmark cross-coupling reaction is presented. The introduction of silylcarboxylic acids as bifunctional reagents (CO and nucleophile source) avoids the need for external gaseous CO and a silylarene coupling partner. The transformation features high functional group tolerance and it is successful with electron-rich, -neutral, and -poor aryl iodides. Stoichiometric studies and control experiments provide insight into the reaction mechanism and support the hypothesized dual role of silylcarboxylic acids. (Figure presented.).
- Li, Xiong,Xu, Jie,Li, Yue,Kramer, S?ren,Skrydstrup, Troels,Lian, Zhong
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p. 4078 - 4083
(2020/07/30)
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- Synthesis of diaryl ketones through oxidative cleavage of the C-C double bonds in N -Sulfonyl enamides
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An oxidative cleavage of a C-C double bond is developed from the photochemical [2+2]-cycloaddition of diaryl N-tosyl enamides, aryl heteroaryl N-tosyl enamides, and N-tosyl cyclic enamides with singlet molecular oxygen, followed by a ring-opening reaction mediated by Cs2CO3 under air and sunlight without the use of photosesitizer, producing symmetrical and unsymmetrical diaryl, heterodiaryl, and cyclic ketones in good to excellent yields. Moreover, the oxidative cleavage of C-C triple bonds from 1-alkynes is demonstrated for the synthesis of symmetrical and unsymmetrical ketones from the Cu-catalyzed [3+2]-cycloaddition, Rh-catalyzed alkoxyarylation, photooxygenation, and ring-opening reaction in one-pot. Because the synthesis of the symmetrical and unsymmetrical diaryl and/or heterodiaryl ketones bearing an electron-donating group is not easy, the present method is notable.
- Kim, Hyunseok,Park, Sangjune,Baek, Yonghyeon,Um, Kyusik,Han, Gi Uk,Jeon, Da-Hye,Han, Sang Hoon,Lee, Phil Ho
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p. 3486 - 3496
(2018/04/14)
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- PHOTOACTIVATABLE FOULING-RESISTANT COPOLYMERS
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A photoactivatable fouling-resistant copolymer composed of a photoactivatable monomer and a hydrophilic monomer is disclosed. The photoactivatable monomer includes an aryl ketone derivative having one or more polar groups or alkyl groups.
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Paragraph 00148; 00151
(2017/03/14)
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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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- Iron-catalyzed carbonylation of aryl halides with arylborons using stoichiometric chloroform as the carbon monoxide source
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A general iron-catalyzed carbonylative Suzuki-Miyaura coupling of aryl halides with arylborons is reported, using stoichiometric CHCl3 as the CO source. The high efficiency, economy, selectivity, and operational simplicity of this transformation make this method a valuable tool in organic synthesis. Importantly, the presented strategy allows effective 13C labeling simply by using the commercially available 13C-labeled CHCl3. On the basis of the initial mechanistic exploration, an aryl radical intermediate is proposed in the present carbonylation process.
- Zhao, Hongyuan,Du, Hongyan,Yuan, Xiaorong,Wang, Tianjiao,Han, Wei
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supporting information
p. 5782 - 5787
(2016/11/06)
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- KCC-1 supported palladium nanoparticles as an efficient and sustainable nanocatalyst for carbonylative Suzuki-Miyaura cross-coupling
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This work reports a cost-effective and sustainable protocol for the carbonylative Suzuki-Miyaura cross-coupling reaction catalyzed by palladium nanoparticles (Pd NPs) supported on fibrous nanosilica (KCC-1). Under mild reaction conditions, the KCC-1-PEI/Pd catalytic system showed a turnover number (TON) 28-times and a turnover frequency (TOF) 51-times higher than the best supported Pd catalyst reported in the literature for the carbonylative cross-coupling between 4-iodoanisole and phenylboronic acid, as a test reaction. Also, the catalyst could be recycled up to ten times with a marginal loss in activity after the eighth cycle. The high activity of the catalyst can be attributed to the fibrous nature of the KCC-1 support and PEI functionalization provided the enhanced stability.
- Gautam, Prashant,Dhiman, Mahak,Polshettiwar, Vivek,Bhanage, Bhalchandra M.
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supporting information
p. 5890 - 5899
(2016/11/06)
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- Palladacycle-Catalyzed Carbonylative Suzuki-Miyaura Coupling with High Turnover Number and Turnover Frequency
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This work reports the carbonylative Suzuki-Miyaura coupling of aryl iodides catalyzed by palladacycles. More importantly, the palladacycles have been used to generate high turnover numbers (TON's) and turnover frequencies (TOF's). A range of aryl iodides can be coupled with arylboronic acids, generating TON's in the range of 106 to 107 and TOF's in the range of 105 to 106 h-1. Comparison of the palladacycles with a conventional palladium source shows their superiority in generating high TON's and TOF's.
- Gautam, Prashant,Bhanage, Bhalchandra M.
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p. 7810 - 7815
(2015/08/18)
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- Palladium-catalyzed cross-coupling of 2-aryl-1,3-dithianes
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Palladium-catalyzed cross-coupling of aryl bromides with 2-aryl-1,3-dithianes is described. This methodology takes advantage of the relatively acidic benzylic proton of the dithiane, allowing it to act as a competent, polarity-reversed transmetalation reagent. This unique approach affords the ability to employ an orthogonal deprotection strategy, and practical routes to both diaryl ketones and diarylmethanes are illustrated. Cross-coupling of a range of aryl dithianes with aryl bromides, including scope and current limitations, is presented.
- Dockrey, Summer A. Baker,Makepeace, Alicia K.,Schmink, Jason R.
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p. 4730 - 4733
(2015/04/27)
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- Nickel-catalyzed cross-coupling of carboxylic anhydrides with arylboronic acids
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A nickel-based catalyst was employed in the cross-coupling of carboxylic anhydrides with arylboronic acids, and the reaction was carried out under mild conditions. This new protocol provides an efficient, cheap and convenient alternative to synthesizing aromatic ketones.
- Chen, Qiang,Fan, Xin-Heng,Zhang, Li-Peng,Yang, Lian-Ming
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p. 53885 - 53890
(2015/01/16)
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- Experimental and DFT study on the indium-mediated synthesis of benzophenones via arylstannanes
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Experimental results of the solvent-free, indium-promoted reaction of aroyl chlorides with arylstannanes showed a narrow scope; its efficiency depends both on the extent of methylation in the latter and on the nature, number and position of the substituents in the former. With the purpose of explaining experimental results, a theoretical analysis with DFT methods was performed for a set of selected cases. This journal is
- Lo Fiego, Marcos J.,Dorn, Viviana B.,Badajoz, Mercedes A.,Lockhart, Mara T.,Chopa, Alicia B.
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p. 49079 - 49085
(2014/12/10)
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- One-pot synthesis of diarylmethanones through palladium-catalyzed sequential coupling and aerobic oxidation of aryl bromides with acetophenone as a latent carbonyl donor
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A one-pot palladium-catalyzed synthesis of symmetrical and unsymmetrical diarylmethanones using acetophenone and aryl bromides as raw materials has been developed. In this reaction, acetophenone acts as a latent carbonyl donor and two pathways of palladium-catalyzed sequential coupling and aerobic oxidation are identified. The reaction is applicable to a spectrum of substrates and delivers the products in moderate to good yields. This method can be used for the synthesis of ketoprofen, a nonsteroidal anti-inflammatory drug, in a two-step procedure and 45% overall yield.
- Wang, Xing,Liu, Fu-Di,Tu, Hai-Yang,Zhang, Ai-Dong
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p. 6554 - 6562
(2014/08/05)
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- Carbonylative suzuki couplings of aryl bromides with boronic acid derivatives under base-free conditions
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The carbonylative Suzuki-Miyaura reaction between aryl bromides and arylboronic acid equivalents is herein reported, using base-free conditions and a limited excess of carbon monoxide generated ex situ from stable CO-precursors. Under these conditions, unsymmetrical biaryl ketones were obtained in modest to excellent yields. This method was adapted to the synthesis of the triglyceride and cholesterol regulator drug, fenofibrate, and its 13C-labeled derivative in good yields from the appropriate CO-precursor.
- Bjerglund, Klaus M.,Skrydstrup, Troels,Molander, Gary A.
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supporting information
p. 1888 - 1891
(2014/05/06)
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- A Palladium Bipyridyl Complex Grafted onto Nanosized MCM-41 as a Heterogeneous Catalyst for Negishi Coupling
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The Negishi coupling of aryl bromides or acyl chlorides with organozinc chlorides catalyzed by a palladium bipyridyl complex anchored on nanosized mobile crystalline material 41 (MCM-41) were investigated. The reactions proceeded smoothly with a very low catalyst loading in THF at 70°C for electron-deficient aryl bromides, which gave good to high yields of the Negishi coupling products. However, reactions in toluene at 110°C were required if electron-rich aryl bromides were employed. For acyl chlorides, the reactions could be performed in THF at 50°C and the corresponding ketones and ynones were obtained in high yields. After centrifugation, it was possible to easily recover the supported catalyst from the reaction mixture, and this could be reused several times without any retreatment or regeneration with only a slight decrease in activity.
- Wu, Wei-Yi,Lin, Tze-Chiao,Takahashi, Tamotsu,Tsai, Fu-Yu,Mou, Chung-Yuan
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p. 1011 - 1019
(2013/05/09)
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- NHC-Pd(II)-Im (NHC=N-heterocyclic carbene, Im=1-methylimidazole) complex catalyzed coupling reaction of arylboronic acids with carboxylic acid anhydrides in water
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A well-defined N-heterocyclic carbene (NHC)-palladium chloride-imidazole complex exhibited high catalytic activity in the coupling reaction of arylboronic acids with carboxylic acid anhydrides in pure water under mild conditions. Under the optimal conditions, all reactions gave the desired coupling products in moderate to high yields.
- Lin, Xiao-Fang,Li, Yao,Li, Shuang-Yan,Xiao, Zheng-Kang,Lu, Jian-Mei
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experimental part
p. 5806 - 5809
(2012/09/08)
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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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- New synthesis of biaryls via Rh-catalyzed decarbonylative Suzuki-coupling of carboxylic anhydrides with arylboroxines
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The catalytic cross-coupling of aromatic carboxylic anhydrides or acid chlorides with triarylboroxines has been achieved for the first time under decarbonylation, giving rise to the unsymmetrical biaryls rather than the expected diaryl ketones. This new decarbonylative Suzuki coupling, catalyzed by a [Rh(ethylene)2Cl]2/KF system, can be applied to aromatic, heteroaromatic and vinylic carboxylic anhydrides, potentially opening up new perspectives for the use of carboxylic acid derivatives as substrates in biaryl syntheses.
- Goossen,Paetzold
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p. 1665 - 1668
(2007/10/03)
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- Synthesis and structure-activity relationship for new series of 4-phenoxyquinoline derivatives as specific inhibitors of platelet-derived growth factor receptor tyrosine kinase
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We discovered a new series of 4-phenoxyquinoline derivatives as potent and selective inhibitors of the platelet-derived growth factor receptor (PDGFr) tyrosine kinase. We researched the highly potent and selective inhibitors on the basis of both PDGFr and epidermal growth factor receptor (EGFr) inhibitory activity. First, we found a compound, Ki6783 (1), which inhibited PDGFr autophosphorylation at 0.13 μM, but it did not inhibit EGFr autophosphorylation at 100 μM. After extensive explorations, we found the two desired compounds, Ki6896 (2) and Ki6945 (3), which are substituted by benzoyl and benzamide at the 4-position of the phenoxy group on 4-phenoxyquinoline, respectively. These inhibitory activities were 0.31 and 0.050 μM, respectively, but neither of them inhibited EGFr autophosphorylation at 100 μM. We further investigated the profile of both compounds toward various tyrosine and serine/threonine kinases. The three compounds specifically inhibited PDGFr rather than the other kinases.
- Kubo, Kazuo,Ohyama, Shin-Ichi,Shimizu, Toshiyuki,Takami, Atsuya,Murooka, Hideko,Nishitoba, Tsuyoshi,Kato, Shinichiro,Yagi, Mikio,Kobayashi, Yoshiko,Iinuma, Noriko,Isoe, Toshiyuki,Nakamura, Kazuhide,Iijima, Hiroshi,Osawa, Tatsushi,Izawa, Toshio
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p. 5117 - 5133
(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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- Substituted benzoylbenzene-, biphenyl- and 2-oxazole- alkanoic acid compounds
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There are disclosed substituted benzoylbenzene-, biphenyl- and 2-oxazole- alkanoic acid derivatives and the pharmacologically acceptable salts thereof as inhibitors of PLA2 and lipoxygenase, and their use in the treatment of inflammatory condit
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- Substituted benzoylbenzene-, biphenyl- and 2-oxazole-alkanoic acid derivatives as inhibitors of pla2 and lipoxygenase
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There are disclosed compounds of the formula wherein A is a group having the formula STR1 wherein X is --N-- or STR2 Z is STR3 R1 is hydrogen, lower alkyl or phenyl; R2 is hydrogen or lower alkyl; or R1 and R2 taken together form a benzene ring, with the proviso that when X is --N--, Z is other than STR4 R3 is hydrogen or lower alkyl; n is 1-2; B is STR5 wherein Y is OR5 or N(OH)R8 ; R4 and R5 are each, independently, hydrogen or lower alkyl; R6 is hydrogen, halo or nitro; R7 is STR6 R8 is lower alkyl; m is 0-3; and the pharmacologically acceptable salts thereof, and their use in the treatment of inflammatory conditions, such as rheumatoid arthritis, ulcerative colitis, psoriasis and other immediate hypersensitivity reactions; in the treatment of leukotriene-mediated naso-bronchial obstructive air-passageway conditions, such as allergic rhinitis, allergic bronchial asthma and the like; and as gastric cytoprotective agents.
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- Substituted benzoylbenzene-, biphenyl- and 2-oxazole-alkanoic acid derivatives
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There are disclosed compounds of the formula wherein A is STR1 n is 1-2; B is STR2 wherein R4 and R5 are each, independently, hydrogen or lower alkyl; R6 is hydrogen, halo or nitro; STR3 R8 is lower alkyl; m is
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- Trifluoroacetic Acid-catalysed Transacylation of Arenes by Acylpentamethylbenzene
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Facile transacylation between acylpentamethylbenzene and activated arenes such as anisole was found to occur in boiling trifluoroacetic acid (TFA).The mechanism for the transacylation between acetylpentamethylbenzene (AcPMB) and anisole with TFA was elucidated by means of product isolation and kinetics.The reaction proceeds via reversible protodeacetylation of AcPMB involving an ipso-protonated intermediate B to give pentamethylbenzene and acetic trifluoroacetic anhydride followed by irreversible acetylation of anisole by the mixed anhydride.The mechanism resulting in an ipso-protonated intermediate B was deduced from the reaction of acetylmesitylene with TFA as well as from the rate of deacetylation of 3,5-dideuterioacetylmesitylene with TFA.The formation of such an intermediate was also independently confirmed by 13C n.m.r. spectroscopic syudies on AcPMB in superacid solutions under stable conditions.
- Keumi, Takashi,Morita, Toshio,Shimada, Takanobu,Teshima, Naomi,Kitajima, Hidehiko,Prakash, G. K. Surya
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p. 847 - 852
(2007/10/02)
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