- Arylketones as Aryl Donors in Palladium-Catalyzed Suzuki-Miyaura Couplings
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Herein, we report the arylation, alkylation, and alkenylation of aryl ketones via a palladium-catalyzed Suzuki-Miyaura cross-coupling reaction. The use of the pyridine-oxazoline ligand is the key to the cleavage of the unstrained C-C bond. The late-stage arylation of aryl ketones derived from drugs and natural products demonstrated the synthetic utility of this protocol.
- Wang, Zhen-Yu,Ma, Biao,Xu, Hui,Wang, Xing,Zhang, Xu,Dai, Hui-Xiong
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p. 8291 - 8295
(2021/11/13)
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- Impact of Solvent and Their Contaminants on Pd/C Catalyzed Suzuki-Miyaura Cross-Coupling Reactions
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The aim of this work was to understand if solvent contaminants can interfere in Suzuki’s cross-coupling reactions and if it can explain the lack of robustness in industrial processes. For this purpose, several parameters were tested on the industrial model reaction between 2-bromonaphthalene and phenylboronic acid catalyzed by Pd/C. Best results were obtained using THF as solvent. Traces of the precursors of the used solvents, such as 2,3-dihydrofurane or maleic anhydride (100–300 ppm related to the solvent) strongly poisoned the reaction, decreasing the conversion significantly. This means that to ensure robust production, solvent quality must be analyzed at the ppm level. Fortunately, addition of triphenylphosphine can circumvent the catalyst poisoning.
- de Lambert de Boisjan, Alexandre,Allemann, Christophe,Fadini, Luca
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- Desulfurization of Diaryl(heteroaryl) Sulfoxides with Benzyne
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Two benzyne-enabled desulfurization reactions have been demonstrated which convert diaryl sulfoxides and heteroaryl sulfoxides to biaryls and desulfurized heteroarenes, respectively. The reaction accessing biaryls tolerates a variety of functional groups, such as halides, pseudohalides, and carbonyls. Mechanistic studies reveal that both reactions proceed via a common assembly process but divergent disassemblies of the generated tetraaryl(heteroaryl) sulfuranes.
- Chen, De-Li,Sun, Yan,Chen, Mengyuan,Li, Xiaojin,Zhang, Lei,Huang, Xin,Bai, Yihui,Luo, Fang,Peng, Bo
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supporting information
(2019/06/13)
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- Nickel-Catalyzed Kumada Coupling of Boc-Activated Aromatic Amines via Nondirected Selective Aryl C-N Bond Cleavage
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A nickel-catalyzed Kumada coupling of aniline derivatives was developed by selective cleavage of aryl C-N bonds under mild reaction conditions. Without preinstallation of an ortho directing group on anilines, the cross-coupling reactions of Boc-protected aromatic amines with aryl Grignard reagents afforded unsymmetric biaryls. Mechanistic studies by DFT calculations revealed that the nickel-mediated C-N bond cleavage is the rate-limiting step.
- Zhang, Zheng-Bing,Ji, Chong-Lei,Yang, Ce,Chen, Jie,Hong, Xin,Xia, Ji-Bao
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supporting information
p. 1226 - 1231
(2019/02/14)
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- Room-Temperature Aqueous Suzuki-Miyaura Cross-Coupling Reactions Catalyzed via a Recyclable Palladium@Halloysite Nanocomposite
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A reliable method for encapsulation of palladium nanoparticles (6-8 nm particles) in halloysite (Pd@Hal) has been developed. The Pd@Hal was found to be a highly efficient room-temperature catalyst for Suzuki-Miyaura cross-coupling reactions that gave high yields of a diverse array of coupling products in 5:2 n-PrOH/H2O within 1 h. The catalytic system was remarkably effective with a broad substrate scope. In addition, the catalyst was easily recovered and recycled without a significant loss of catalytic activity.
- Hamdi, Jumanah,Blanco, Alexis A.,Diehl, Brooke,Wiley, John B.,Trudell, Mark L.
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supporting information
p. 3471 - 3475
(2019/04/25)
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- Chromium-Catalyzed Regioselective Kumada Arylative Cross-Coupling of C(aryl)-O Bonds with a Traceless Activation Strategy
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We report here the chromium-catalyzed regioselective Kumada arylative cross-coupling of C(aryl)-O bonds at ambient temperature. By using a simple and low-cost chromium(II) chloride salt as a precatalyst, accompanied by a 2-pyridyl ligation, the catalytic cleavage and arylative coupling of C(aryl)-O bonds were achieved with a traceless activation strategy, overcoming the regioselectivity obstacle when several C-O bonds coexist in the Kumada coupling system.
- Fan, Fei,Tang, Jinghua,Luo, Meiming,Zeng, Xiaoming
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p. 13549 - 13559
(2018/10/31)
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- Nickel-Catalyzed Csp2-Csp3 Bond Formation via C-F Bond Activation
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A nickel-catalyzed cross coupling of aryl fluorides via C-F bond activation has been developed. The alkylation method allows selective replacement of aryl fluorides by alkyl groups and enables the synthesis of diverse and otherwise difficult to access scaffolds in good yields.
- Ho, Yee Ann,Leiendecker, Matthias,Liu, Xiangqian,Wang, Chengming,Alandini, Nurtalya,Rueping, Magnus
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supporting information
p. 5644 - 5647
(2018/09/12)
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- Modular Functionalization of Arenes in a Triply Selective Sequence: Rapid C(sp2) and C(sp3) Coupling of C?Br, C?OTf, and C?Cl Bonds Enabled by a Single Palladium(I) Dimer
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Full control over multiple competing coupling sites would enable straightforward access to densely functionalized compound libraries. Historically, the site selection in Pd0-catalyzed functionalizations of poly(pseudo)halogenated arenes has been unpredictable, being dependent on the employed catalyst, the reaction conditions, and the substrate itself. Building on our previous report of C?Br-selective functionalization in the presence of C?OTf and C?Cl bonds, we herein complete the sequence and demonstrate the first general arylations and alkylations of C?OTf bonds (in I dimer. This allowed the realization of the first general and triply selective sequential C?C coupling (in 2D and 3D space) of C?Br followed by C?OTf and then C?Cl bonds.
- Keaveney, Sinead T.,Kundu, Gourab,Schoenebeck, Franziska
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supporting information
p. 12573 - 12577
(2018/09/18)
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- Cross-Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C?O or C?N Bond Cleavage
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Various aryl-, alkenyl-, and/or alkyllithium species reacted smoothly with aryl and/or benzyl ethers with cleavage of the inert C?O bond to afford cross-coupled products, catalyzed by commercially available [Ni(cod)2] (cod=1,5-cyclooctadiene) catalysts with N-heterocyclic carbene (NHC) ligands. Furthermore, the coupling reaction between the aryllithium compounds and aryl ammonium salts proceeded under mild conditions with C?N bond cleavage in the presence of a [Pd(PPh3)2Cl2] catalyst. These methods enable selective sequential functionalizations of arenes having both C?N and C?O bonds in one pot.
- Yang, Ze-Kun,Wang, Dong-Yu,Minami, Hiroki,Ogawa, Hiroyuki,Ozaki, Takashi,Saito, Tatsuo,Miyamoto, Kazunori,Wang, Chao,Uchiyama, Masanobu
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supporting information
p. 15693 - 15699
(2016/10/25)
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- Nickel/N-Heterocyclic Carbene-Catalyzed Suzuki-Miyaura Type Cross-Coupling of Aryl Carbamates
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The utility of N-heterocyclic carbene ligands in nickel-catalyzed Suzuki-Miyaura cross-coupling of aryl esters and carbamates is investigated. Imidazol-2-ylidene bearing 2-adamantyl groups at its nitrogen atoms generates the most active nickel species among the ligands examined, allowing cross-coupling of a range of aryl carbamates and pivalates. Unlike the previously reported system using tricyclohexylphosphine, this protocol is suitable for the cross-coupling using arylboronic esters in addition to arylboronic acids.
- Ohtsuki, Akimichi,Yanagisawa, Kousuke,Furukawa, Takayuki,Tobisu, Mamoru,Chatani, Naoto
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p. 9409 - 9414
(2016/10/17)
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- The Missing C1-C5 Cycloaromatization Reaction: Triplet State Antiaromaticity Relief and Self-Terminating Photorelease of Formaldehyde for Synthesis of Fulvenes from Enynes
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The last missing example of the four archetypical cycloaromatizations of enediynes and enynes was discovered by combining a twisted alkene excited state with a new self-terminating path for intramolecular conversion of diradicals into closed-shell products. Photoexcitation of aromatic enynes to a twisted alkene triplet state creates a unique stereoelectronic situation, which is facilitated by the relief of excited state antiaromaticity of the benzene ring. This enables the usually unfavorable 5-endo-trig cyclization and merges it with 5-exo-dig closure. The 1,4-diradical product of the C1-C5 cyclization undergoes internal H atom transfer that is coupled with the fragmentation of an exocyclic C-C bond. This sequence provides efficient access to benzofulvenes from enynes and expands the utility of self-terminating aromatizing enyne cascades to photochemical reactions. The key feature of this self-terminating reaction is that, despite the involvement of radical species in the key cyclization step, no external radical sources or quenchers are needed to provide the products. In these cascades, both radical centers are formed transiently and converted to the closed-shell products via intramolecular H-transfer and C-C bond fragmentation. Furthermore, incorporating C-C bond cleavage into the photochemical self-terminating cyclizations of enynes opens a new way for the use of alkenes as alkyne equivalents in organic synthesis.
- Mohamed, Rana K.,Mondal, Sayantan,Jorner, Kjell,Delgado, Thais Faria,Lobodin, Vladislav V.,Ottosson, Henrik,Alabugin, Igor V.
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supporting information
p. 15441 - 15450
(2015/12/26)
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- Triarylphosphines as Aryl Donors for Pd(II)-Catalyzed Aromatic Coupling of Oxabenzonorbornadienes
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A new approach was developed for Pd(II)-catalyzed aromatic coupling of oxabenzonorbornadienes with triarylphosphines as both ligands and aryl donors. Diverse functional groups including halo- (F-, Cl-, and Br-), CF3-, and furyl groups are well tolerated. For unsymmetrical triarylphosphines, the migration ability of aryls is consistent with the electronic property of substituents and maintains the order EDG-Ar > H-Ar > EWD-Ar (EDG means electron-donating group, EWG means electron-withdrawing group). A preliminary mechanistic study was also disclosed.
- Zhou, Hui,Li, Jixing,Yang, Huameng,Xia, Chungu,Jiang, Gaoxi
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supporting information
p. 4628 - 4631
(2015/09/28)
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- Organoaluminum-Mediated Direct Cross-Coupling Reactions
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We present a direct cross-coupling reaction between arylaluminum compounds (ArAlMe2·LiCl) and organic halides RX (R=aryl, alkenyl, alkynyl; X=I, Br, and Cl) without any external catalyst. The reaction takes place smoothly, simply upon heating, thereby enabling the efficient and chemo-/stereoselective formation of biaryl, alkene, and alkyne coupling products with broad functional group compatibility.
- Minami, Hiroki,Saito, Tatsuo,Wang, Chao,Uchiyama, Masanobu
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p. 4665 - 4668
(2015/04/14)
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- Alkenes as alkyne equivalents in radical cascades terminated by fragmentations: Overcoming stereoelectronic restrictions on ring expansions for the preparation of expanded polyaromatics
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Chemoselective interaction of aromatic enynes with Bu3Sn radicals can be harnessed for selective cascade transformations, yielding either Sn-substituted naphthalenes or Sn-indenes. Depending on the substitution at the alkene terminus, the initial regioselective 5-exo-trig cyclizations can be intercepted at the 5-exo stage via either hydrogen atom abstraction or C-S bond scission or allowed to proceed further to the formal 6-endo products via homoallylic ring expansion. Aromatization of the latter occurs via β-C-C bond scission, which is facilitated by 2c,3e through-bond interactions, a new stereoelectronic effect in radical chemistry. The combination of formal 6-endo-trig cyclization with stereoelectronically optimized fragmentation allows the use of alkenes as synthetic equivalents of alkynes and opens a convenient route to α-Sn-substituted naphthalenes, a unique launching platform for the preparation of extended polyaromatics.
- Mohamed, Rana K.,Mondal, Sayantan,Gold, Brian,Evoniuk, Christopher J.,Banerjee, Tanmay,Hanson, Kenneth,Alabugin, Igor V.
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supporting information
p. 6335 - 6349
(2015/06/02)
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- Iron-catalyzed coupling of aryl sulfamates and aryl/vinyl tosylates with aryl grignards
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The iron-catalyzed coupling of aryl sulfamates and tosylates with aryl Grignard reagents is reported for the first time. The methodology employs air-stable, low-cost FeF3·3H2O and the N-heterocyclic carbene ligand IPr·HCl as the preligand to form a long-lived catalyst upon treatment with aryl Grignards. The reaction provides a range of cross-coupled products in good-to-excellent yields. In contrast to previous reports with aryl chlorides, these reactions proceed with low levels of Grignard homocoupling regardless of the iron source.
- Agrawal, Toolika,Cook, Silas P.
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supporting information
p. 5080 - 5083
(2014/12/11)
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- Improved procedure for single-electron-transfer-induced grignard cross-coupling reaction
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Aryl Grignard reagents were found to undergo coupling with aryl or alkenyl bromides in the presence of LiCl in a mixed solvent consisting of toluene and THF (2/1). Previously employed removal of THF with evacuation from Grignard solutions is no longer needed to obtain biaryls and styrene derivatives.
- Shirakawa, Eiji,Okura, Keisho,Uchiyama, Nanase,Murakami, Takuya,Hayashi, Tamio
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supporting information
p. 922 - 924
(2014/06/23)
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- Platinum-catalyzed C-H arylation of simple arenes
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This report describes the Na2PtCl4 catalyzed C-H arylation of arene substrates with diaryliodonium salts. The site selectivity of these reactions is predominantly controlled by steric factors. Remarkably, Na2PtCl4-catalyzed naphthalene arylation proceeds with opposite site selectivity compared to that obtained with Na2PdCl 4 as the catalyst. Preliminary mechanistic studies provide evidence for a PtII/PtIV catalytic cycle involving rate-limiting C-C bond-forming reductive elimination.
- Wagner, Anna M.,Hickman, Amanda J.,Sanford, Melanie S.
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p. 15710 - 15713
(2013/11/06)
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- Direct C-C bond construction from arylzinc reagents and aryl halides without external catalysts
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Direct cross-coupling between an arylzinc reagent and an aryl halide was accomplished without any external catalyst, enabling efficient and selective formation of the corresponding biaryl compound with broad functional group compatibility. Direct cross-coupling between a diarylzinc compound and an aryl iodide was accomplished without using any external catalyst. The reaction is efficient and selective, enabling formation of the corresponding biaryl compounds with broad functional group compatibility. The reaction is proposed to proceed by a thermally initiated single electron transfer (SET) route. Copyright
- Minami, Hiroki,Wang, Xuan,Wang, Chao,Uchiyama, Masanobu
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supporting information
p. 7891 - 7894
(2014/01/06)
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- Palladium-catalyzed Suzuki-Miyaura coupling of aryl sulfamates with arylboronic acids
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Readily available NHC-Pd(ii)-Mp complexes 2 showed efficient catalytic activity toward the Suzuki-Miyaura coupling of aryl sulfamates with arylboronic acids or potassium phenyltrifluoroborate, giving the expected coupling products in good to high yields.
- Wang, Zhan-Yong,Ma, Qin-Na,Li, Ren-Hao,Shao, Li-Xiong
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p. 7899 - 7906
(2013/11/19)
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- Base- and metal-free C-H direct arylations of naphthalene and other unbiased arenes with diaryliodonium salts
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A novel metal-free direct arylation of unbiased arenes with diaryliodonium triflates in a process where the use of solvents and additives is not required has been established.
- Castro, Susana,Fernandez, Juan J.,Vicente, Ruben,Fananas, Francisco J.,Rodriguez, Felix
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supporting information
p. 9089 - 9091
(2012/11/07)
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- N-heterocyclic carbene-palladium(II)-1-methylimidazole complex-catalyzed Suzuki-Miyaura coupling of aryl sulfonates with arylboronic acids
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A well-defined NHC-Pd(II)-Im complex 1 was found to be an effective catalyst for the Suzuki-Miyaura coupling of aryl sulfonates including tosylates and phenylsulfonates with arylboronic acids, giving the desired coupling products in good to high yields. Acceptable yields can also be achieved even by using the less reactive mesylates as the substrates. It is worthy of noting here that this is the first example of NHC-Pd(II) complex-catalyzed Suzuki-Miyaura coupling of aryl sulfonates with arylboronic acids, enriching an inexpensive, convenient, and alternative method for the synthesis of biaryl compounds.
- Wang, Zhan-Yong,Chen, Gao-Qi,Shao, Li-Xiong
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experimental part
p. 6608 - 6614
(2012/10/07)
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- Nickel-catalyzed cross-coupling of aryl phosphates with arylboronic acids
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The Suzuki-Miyaura cross-coupling of aryl phosphates using Ni(PCy 3)2Cl2 as an inexpensive, bench-stable catalyst is described. Broad substrate scope and high efficiency are demonstrated by the syntheses of more than 40 biaryls and by constructing complex organic molecules. The poor reactivity of aryl phosphates relative to aryl halides is successfully employed to construct polyarenes by selective cross-coupling using Pd and Ni catalysts.
- Chen, Hu,Huang, Zhongbin,Hu, Xiaoming,Tang, Guo,Xu, Pengxiang,Zhao, Yufen,Cheng, Chien-Hong
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experimental part
p. 2338 - 2344
(2011/05/30)
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- Biaryl construction through kumada coupling with diaryl sulfates as one-by-one electrophiles under mild conditions
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(Figure presented) Diaryl sulfates were successfully applied as one-by-one organo electrophiles in Kumada coupling to construct biaryls with the emission of harmless Inorganic salts.
- Guan, Bing-Tao,Lu, Xing-Yu,Zheng, Yang,Yu, Da-Gang,Wu, Tong,Li, Kun-N,Li, Bi-Jie,Shi, Zhang-Jie
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supporting information; experimental part
p. 396 - 399
(2010/03/04)
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- Nickel-catalyzed cross-coupling of aryl methyl ethers with aryl boronic esters
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(Chemical Equation Presented) To C-OMe and go: The title reaction, involving cleavage of a C-OMe bond, is demonstrated for the coupling of aryl methyl ethers on fused aromatic systems, such as naphthalene and phenanthrene, as well as anisoles containing electron-withdrawing groups with a wide range of boronic esters. cod=cycloocta-1,5-diene, Cy=cyclohexyl.
- Tobisu, Mamoru,Shimasaki, Toshiaki,Chatani, Naoto
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experimental part
p. 4866 - 4869
(2009/02/08)
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- Biaryl construction via Ni-catalyzed C-O activation of phenolic carboxylates
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Biaryl scaffolds were constructed via Ni-catalyzed aryl C-O activation by avoiding cleavage of the more reactive acyl C-O bond of aryl carboxylates. Now aryl esters, in general, can be successfully employed in cross-coupling reactions for the first time.
- Guan, Bing-Tao,Wang, Yang,Li, Bi-Jie,Yu, Da-Gang,Shi, Zhang-Jie
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supporting information; scheme or table
p. 14468 - 14470
(2009/02/08)
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- NAPHTHALENE COMPOUND WITH TERMINAL HYDROGEN, LIQUID CRYSTAL COMPOSITION INCLUDING THE COMPOUND, AND LCD DEVICE INCLUDING THE LIQUID CRYSTAL COMPOSITION
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A liquid crystal (LC) compound having generally required physical properties, low viscosity, proper optical anisotropy, proper dielectric anisotropy and good compatibility with other LC compounds is described. An LC composition including the compound and
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Page/Page column 36
(2010/11/26)
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- Gold-catalyzed cyclo-isomerization of 1,6-diyne-4-en-3-ols to form naphthyl ketone derivatives
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We report a new efficient gold-catalyzed cyclization of 1,6-diyne-4-en-3-ols to give naphthyl ketone derivatives under ambient conditions. The value of this cyclization is reflected by its applicability to a wide range of alcohol substrates. The Royal Society of Chemistry.
- Lian, Jian-Jou,Liu, Rai-Shung
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p. 1337 - 1339
(2007/12/27)
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- Addition and Cyclization Reactions in the Thermal Conversion of Hydrocarbons with Enyne Structure, 3. - A Mechanistic Study of the Thermal Cycloisomerization of 1,4-Diphenyl-1-buten-3-yne
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The gas-phase pyrolysis of 1,4-diphenyl-1-buten-3-yne (1) was investigated in the temperature range between 600 and 800 deg C and in the presence of different carrier gases (N2, N2/toluene, H2).By a detailed analysis (GC, GC/MS, GC/FTIR) all volatile reaction products were identified and quantitatively determined.Besides several fragmentation products (substituted benzenes C7-C10) and some carbon-rich deposits the main products are benzene (4), naphthalene (5) as well as 1- (2) and 2-phenylnaphthalene (3).Under similar conditions 4-(4-fluorophenyl)-1-phenyl-1-buten-3-yne (1a) furnished mainly fluorobenzene (4a), naphthalene (5), 1- (2a) and 2-(4-fluorophenyl)naphthalene (3a). - If sufficient H atoms are available in the reactive gas phase the conversion of 1/1a is predominantly controlled by radical processes.The cycloisomerization of 1/1a presumably starts with previously formed vinyl radicals, which might initiate a multi-step reaction cascade involving a 1,x-H shift and homoallyl reactions.However, if the reaction system is poor in H atoms (or other chain carrier radicals), a cycloisomerization path via vinylidene carbene species and their subsequent stabilization by intramolecular 1,6-C,H insertion into 3/3a obviously dominates the reaction events.It is concluded that the 1,2-dihydro-2-phenyl-1-naphthyl radicals 19/19a and the 1,2-dihydro-1-phenyl-2-naphthyl radicals 21/21a are important intermediates which are not only precursors of the aromatics 2/2a and 3/3a but also thought to be key intermediates for the most important degradation products 4/4a and 5. - Key Words: Pyrolysis, gas-phase / Cycloisomerization / Vinyl radical / Vinylidene carbene / Rearrangement, homoallyl
- Hofmann, Joerg,Zimmermann, Gerhard,Homann, Klaus-Heinrich
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p. 841 - 848
(2007/10/02)
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- 2-Naphthyl acetic acid derivatives and compositions and methods thereof
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2-Naphthyl acetic acid derivatives and the corresponding amides, esters, hydroxamic acids and addition salts thereof, optionally substituted at the α-position on the acetic acid moiety and/or at position 6 and/or at positions 1, 4, 7 or 8 on the naphthyl ring and optionally saturated at positions 3 and 4, are anti-inflammatory, analgesic, anti-pyretic and anti-pruritic agents. A pharmaceutical method of effecting treatment of inflammation, pain, pyrexia and pruritus by the administration of naphthyl acetic acid derivatives. A pharmaceutical composition for use in the treatment of the above maladies comprising a naphthyl acetic acid derivative.
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