- Tetraethylphosphorodiamidate-Directed Metalation Group: Directed Ortho and Remote Metalation, Cross Coupling, and Remote Phospha Anionic Fries Rearrangement Reactions
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The linked directed ortho and remote metalation (DoM and DreM) and cross-coupling reactions of aryl phosphorodiamidates (Ar-OP(O)(NEt2)2) is reported. The o-iodo and o-boronato aryl tetraethylphosphorodiamidates 3, prepared by DoM, undergo orthogonal Ni- and Pd-catalyzed Suzuki-Miyaura cross coupling to furnish biaryls 4 and 5 in good to excellent yields. Silicon group protection of biaryl 4 via DoM followed by previously unobserved DreM phospha anionic Fries rearrangement affords biaryls 11 which, under acidic conditions, furnish oxaphosphorine oxides 12.
- Alessi, Manlio,Blackburn, Thomas,Patel, Jignesh J.,Sawinski, Hannah,Snieckus, Victor
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supporting information
(2020/05/18)
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- Potassium trimethylsilanolate enables rapid, homogeneous suzuki-miyaura cross-coupling of boronic esters
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Herein, a mild and operationally simple method for the Suzuki-Miyaura cross-coupling of boronic esters is described. Central to this advance is the use of the organic-soluble base, potassium trimethylsilanolate, which allows for a homogeneous, anhydrous cross-coupling. The coupling proceeds at a rapid rate, often furnishing products in quantitative yield in less than 5 min. By applying this method, a >10-fold decrease in reaction time was observed for three published reactions which required >48 h to reach satisfactory conversion.
- Delaney, Connor P.,Kassel, Vincent M.,Denmark, Scott E.
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- Bis(dialkylphosphino)ferrocene-Ligated Nickel(II) Precatalysts for Suzuki-Miyaura Reactions of Aryl Carbonates
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Aryl carbonates, a common protecting group in synthetic organic chemistry, are potentially valuable electrophiles in cross-coupling reactions. Here, after performing a thorough evaluation of different precatalysts, we demonstrate that (dcypf)Ni(2-ethylphenyl)(Br) (dcypf = 1,1-bis(dicyclohexylphosphino)ferrocene) is an efficient precatalyst for Suzuki-Miyaura reactions using a variety of aryl carbonates as substrates. Mechanistic studies indicate that (dcypf)Ni(2-ethylphenyl)(Br), which contains a bidentate phosphine that binds in a trans geometry, is an effective precatalyst for these reactions for two reasons: (i) it rapidly forms the Ni(0) active species and (ii) it minimizes comproportionation reactions between the Ni(0) active species and both the unactivated Ni(II) precatalyst and on-cycle Ni(II) complexes to form catalytically inactive Ni(I) species. In contrast, the state of the art precatalyst (dppf)Ni(o-tolyl)(Cl) (dppf = 1,1-bis(diphenylphosphino)ferrocene), which contains a bidentate phosphine that binds in a cis geometry, forms Ni(I) species during activation and is essentially inactive for aryl carbonate couplings. Although the exact reasons on a molecular level why the dcypf system is more active than the dppf system are unclear, our results indicate that in general Ni catalysts supported by the dcypf ligand will give better performance for catalytic reactions involving substrates which undergo relatively slow oxidative addition, such as aryl carbonates.
- Barth, Emily L.,Davis, Ryan M.,Mohadjer Beromi, Megan,Walden, Andrew G.,Balcells, David,Brudvig, Gary W.,Dardir, Amira H.,Hazari, Nilay,Lant, Hannah M. C.,Mercado, Brandon Q.,Peczak, Ian L.
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supporting information
p. 3377 - 3387
(2019/09/30)
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- New, potentially chelating NHC ligands; synthesis, complexation studies, and preliminary catalytic evaluation
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Two new N-heterocyclic carbene (NHC) ligands bearing 2-morpholino and 2-piperidinyl naphthyl wingtips were synthesised (2-SIMorNap and 2-SIPipNap). Nuclear magnetic resonance studies, in conjunction with crystal structures and derivatisation of the NHC salts using a chiral counteranion, revealed that the ligand wingtips are oriented anti with respect to each other. From the free carbene, palladium, ruthenium and iridium complexes were prepared. NHC-iridium dicarbonyl complexes were made in order to extract the TEP values for these ligands. The study showed that these NHC ligands are more electron-donating than normal, aryl-substituted NHCs. The palladium complexes were tested in representative Suzuki-Miyaura cross-coupling reactions and compared to the state of the art systems. Ruthenium-catalysed ring-closing metathesis with these ligands was also performed. It was found that Grubbs’ 2nd generation catalyst incorporating 2-SIPipNap did not initiate at room temperature and required heating for RCM to occur.
- Ou, Arnold,Wu, Linglin,Salvador, Alvaro,Sipos, Gellert,Zhao, Guangzhen,Skelton, Brian W.,Sobolev, Alexandre N.,Dorta, Reto
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supporting information
p. 3631 - 3641
(2017/03/22)
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- Revisitation of Organoaluminum Reagents Affords a Versatile Protocol for C-X (X = N, O, F) Bond-Cleavage Cross-Coupling: A Systematic Study
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A revisit of organoaluminum reagents for cross-coupling reactions has opened up several types of C-C bond formation protocols through cleavage of phenolic/alcoholic C-O and C-F and ammonium C-N bonds. Catalyzed by the commercially available NiCl2(PCy3)2 catalyst, these reactions proceed smoothly with a wide range of substrates and broad functional group compatibility, providing a versatile methodology for organoaluminum-mediated cross-coupling processes.
- Ogawa, Hiroyuki,Yang, Ze-Kun,Minami, Hiroki,Kojima, Kumiko,Saito, Tatsuo,Wang, Chao,Uchiyama, Masanobu
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p. 3988 - 3994
(2017/06/19)
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- DFT Studies Provide Mechanistic Insight into Nickel-Catalyzed Cross-Coupling Involving Organoaluminum-Mediated C-O Bond Cleavage
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Density functional theory (DFT) calculations were performed to examine the reaction pathway of Ni-catalyzed cross-coupling with organoaluminum through C-O bond cleavage. The results indicate that the strong Lewis acidity of organoaluminums significantly f
- Yang, Ze-Kun,Wang, Chao,Uchiyama, Masanobu
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p. 2565 - 2568
(2017/11/28)
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- Nickel-mediated decarbonylation of simple unstrained ketones through the cleavage of carbon-carbon bonds
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Despite advances in methods for the decarbonylation of aldehydes, the decarbonylation of ketones has been met with limited success because this process requires the activation of two inert carbon-carbon bonds. All of the decarbonylation reactions of simple unstrained ketones reported to date require the addition of a stoichiometric rhodium complex. We report herein the nickel/N-heterocyclic carbene-mediated decarbonylation of simple diaryl ketones. This reaction shows unique acceleration effects based on the presence of both electron-donating and electron-withdrawing groups.
- Morioka, Toshifumi,Nishizawa, Akihiro,Furukawa, Takayuki,Tobisu, Mamoru,Chatani, Naoto
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supporting information
p. 1416 - 1419
(2017/02/10)
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- Combined Theoretical and Experimental Studies of Nickel-Catalyzed Cross-Coupling of Methoxyarenes with Arylboronic Esters via C-O Bond Cleavage
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Nickel(0)-catalyzed cross-coupling of methoxyarenes through C-O bond activation has been the subject of considerable research because of their favorable features compared with those of the cross-coupling of aryl halides, such as atom economy and efficiency. In 2008, we have reported nickel/PCy3-catalyzed cross-coupling of methoxyarenes with arylboronic esters in which the addition of a stoichiometric base such as CsF is essential for the reaction to proceed. Recently, we have also found that the scope of the substrate in the Suzuki-Miyaura-type cross-coupling of methoxyarenes can be greatly expanded by using 1,3-dicyclohexylimidazol-2-ylidene (ICy) as the ligand. Interestingly, a stoichiometric amount of external base is not required for the nickel/ICy-catalyzed cross-coupling. For the mechanism and origin of the effect of the external base to be elucidated, density functional theory calculations are conducted. In the nickel/PCy3-catalyzed reactions, the activation energy for the oxidative addition of the C(aryl)-OMe bond is too high to occur under the catalytic conditions. However, the oxidative addition process becomes energetically feasible when CsF and an arylboronic ester interact with a Ni(PCy3)2/methoxyarene fragment to form a quaternary complex. In the nickel/ICy-catalyzed reactions, the oxidative addition of the C(aryl)-OMe bond can proceed more easily without the aid of CsF because the nickel-ligand bonds are stronger and therefore stabilize the transition state. The subsequent transmetalation from an Ar-Ni-OMe intermediate is determined to proceed through a pathway with lower energies than those required for β-hydrogen elimination. The overall driving force of the reaction is the reductive elimination to form the carbon-carbon bond.
- Schwarzer, Martin C.,Konno, Ryosuke,Hojo, Takayuki,Ohtsuki, Akimichi,Nakamura, Keisuke,Yasutome, Ayaka,Takahashi, Hiroaki,Shimasaki, Toshiaki,Tobisu, Mamoru,Chatani, Naoto,Mori, Seiji
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supporting information
p. 10347 - 10358
(2017/08/10)
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- Synthesis of Biaryls through Nickel-Catalyzed Suzuki-Miyaura Coupling of Amides by Carbon-Nitrogen Bond Cleavage
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The first Ni-catalyzed Suzuki-Miyaura coupling of amides for the synthesis of widely occurring biaryl compounds through N-C amide bond activation is reported. The reaction tolerates a wide range of electron-withdrawing, electron-neutral, and electron-donating substituents on both coupling partners. The reaction constitutes the first example of the Ni-catalyzed generation of aryl electrophiles from bench-stable amides with potential applications for a broad range of organometallic reactions. Breaking and making: The first nickel-catalyzed Suzuki-Miyaura coupling of amides for the synthesis of biaryl compounds through N-C amide bond cleavage is reported. The reaction tolerates a wide range of sensitive and electronically diverse substituents on both coupling partners.
- Shi, Shicheng,Meng, Guangrong,Szostak, Michal
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p. 6959 - 6963
(2016/06/13)
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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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- Rhodium-catalyzed cross-coupling of aryl carbamates with arylboron reagents
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A new method has been developed for the rhodium-catalyzed cross-coupling of aryl carbamates with organoboron reagents. The use of an NHC ligand bearing a 2-adamantyl group, i.e., I(2-Ad), is essential to the success of the reaction. The reaction involves the rhodium-mediated activation of the relatively inert C(aryl)-O bond of aryl carbamates.
- Nakamura, Keisuke,Yasui, Kosuke,Tobisu, Mamoru,Chatani, Naoto
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p. 4484 - 4489
(2015/03/30)
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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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- Single-electron-transfer-induced coupling of arylzinc reagents with aryl and alkenyl halides
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Arylzinc reagents, prepared from aryl halides/zinc powder or aryl Grignard reagents/zinc chloride, were found to undergo coupling with aryl and alkenyl halides without the aid of transition-metal catalysis to give biaryls and styrene derivatives, respectively. In this context, we have already reported the corresponding reaction using aryl Grignard reagents instead of arylzinc reagents. Compared with the Grignard cross-coupling, the present reaction features high functional-group tolerance, whereby electrophilic groups such as alkoxycarbonyl and cyano groups are compatible as substituents on both the arylzinc reagents and the aryl halides. Aryl halides receive a single electron and thereby become activated as the corresponding anion radicals, which react with arylzinc reagents, thus leading to the cross-coupling products. Arylzinc reagents were found to undergo coupling with aryl and alkenyl halides to give biaryl and styrene derivatives, respectively. The cross-coupling, which features high functional-group tolerance, proceeds through a single-electron-transfer mechanism and thus does not require the aid of transition-metal catalysis.
- Shirakawa, Eiji,Tamakuni, Fumiko,Kusano, Eugene,Uchiyama, Nanase,Konagaya, Wataru,Watabe, Ryo,Hayashi, Tamio
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supporting information
p. 521 - 525
(2014/01/23)
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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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- An improvement of nickel catalyst for cross-coupling reaction of arylboronic acids with aryl carbonates by using a ferrocenyl bisphosphine ligand
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Aryl carbonates work as electrophilic substrates for the SuzukiMiyaura reaction in the presence of the nickel catalyst, which is generated from [Ni(cod)2] and ferrocenyl bisphosphine, DCyPF. The nickel catalyst allowed the cross-coupling reaction of arylboronic acids with non-benzo-fused aryl carbonates as well as naphthyl substrates.
- Kuwano, Ryoichi,Shimizu, Ryosuke
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p. 913 - 915
(2011/12/05)
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- Mutual activation: Suzuki-Miyaura coupling through direct cleavage of the sp2 C-O bond of naphtholate
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Working together: A new approach of mutual activation between naphtholates and aryl boronic acid derivatives by the formation of borates to facilitate the Suzuki-Miyaura coupling through direct cleavage of the sp2 C-O bond by nickel catalysis is described (see scheme; R′: annulated ring system). Various naphtholates and aryl boronic acid derivatives could be directly coupled in good yields. Copyright
- Yu, Da-Gang,Shi, Zhang-Jie
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supporting information; experimental part
p. 7097 - 7100
(2011/09/30)
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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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- Rapid nickel-catalyzed suzuki-miyaura cross-couplings of aryl carbamates and sulfamates utilizing microwave heating
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High-speed and scalable nickel-catalyzed cross-coupling of arylboronic acids with aryl carbamates and sulfamates is achieved by using sealed-vessel microwave processing.(Figure Presented)
- Baghbanzadeh, Mostafa,Pilger, Christian,Kappe, C. Oliver
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supporting information; experimental part
p. 1507 - 1510
(2011/04/26)
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- Decarboxylative cross-coupling of aryl tosylates with aromatic carboxylate salts
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(Figure Presented) A bimetallic copper/palladium catalyst system is disclosed that enables the use of tosylates as carbon electrophiles in decarboxylative coupling reactions. A variety of aromatic carboxylate salts, regardless of their substitution pattern, have been coupled with these inexpensive and readily available electrophiles to give the corresponding biaryl compounds in good yields (see scheme).
- Goossen, Luksa J.,Rodriguez, Nuria,Lange, Paul P.,Linder, Christophe
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supporting information; experimental part
p. 1111 - 1114
(2010/04/29)
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- Carbon - Carbon formation via Ni-catalyzed suzuki - Miyaura coupling through C - CN bond cleavage of aryl nitrile
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The Suzuki-Miyaura coupling of aryl nitriles with aryl/alkenyl boronic esters is reported. With this method, the cyano group could be applied as a protecting group of arenes and finally as a leaving group to further construct polyaryl scaffolds.
- Yu, Da-Gang,Yu, Miao,Guan, Bing-Tao,Li, Bi-Jie,Zheng, Yang,Wu, Zhen-Hua,Shi, Zhang-Jie
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supporting information; scheme or table
p. 3374 - 3377
(2009/12/01)
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- Palladium-indolylphosphine-catalyzed hiyama cross-coupling of aryl mesylates
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(Chemical Equation Presented) Aryl mesylates are found to be applicable as electrophiles in organosilicon-mediated coupling reactions. The catalyst system comprising 2 mol % of Pd(OAc)2 and CM-phos supporting ligand is highly effective in catalyzing Hiyama cross-coupling of various aryl and heteroaryl mesylates. Interesting acid additive effects show that the presence of 0.25-0.50 equiv of acetic acid efficiently suppresses the mesylate decomposition and generally promotes the coupling product yields.
- So, Chau Ming,Lee, Hang Wai,Lau, Chak Po,Kwong, Fuk Yee
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supporting information; experimental part
p. 317 - 320
(2009/07/04)
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- Palladacycle-catalyzed highly efficient kinetic resolution of 1-hydroxy-2-aryl-1,2-dihydronaphthalenes via dehydration reaction
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(Chemical Equation Presented) Palladacycles showed their high efficiency in the kinetic resolution of 1-hydroxy-2-aryl-1,2-dihydronaphthalenes via dehydration, providing optically active products in high yields and high ee with an S factor up to 26. The superiority of a benzylic-substituted palladacycle in asymmetric induction was also demonstrated.
- Zhang, Ting-Ke,Mo, Dong-Liang,Dai, Li-Xin,Hou, Xue-Long
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supporting information; experimental part
p. 5337 - 5340
(2009/06/06)
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- Palladium-catalyzed hiyama cross-coupling reactions of aryl mesylates
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(Chemical Equation Presented) The combination of palladium acetate with XPhos shows high efficiency in the Hiyama cross-coupling reactions of aryl mesylates with arylsilanes. The reactions proceed smoothly to generate the corresponding biaryl compounds in
- Zhang, Liang,Qing, Jiang,Yang, Pengyuan,Wu, Jie
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supporting information; experimental part
p. 4971 - 4974
(2009/05/07)
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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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- Palladium-catalyzed Suzuki-Miyaura reactions of potassium aryl- and heteroaryltrifluoroborates with aryl- and heteroaryl triflates
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The Suzuki-Miyaura cross-coupling of potassium aryl-and heteroaryltrifluoroborates with aryl- and heteroaryl triflates is reported. The catalyst system provides good to excellent yields using sterically hindered and electronically diverse coupling partners. Georg Thieme Verlag Stuttgart.
- Molander, Gary A.,Petrillo, Daniel E.,Landzberg, Nicole R.,Rohanna, John C.,Biolatto, Betina
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p. 1763 - 1766
(2007/10/03)
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- An amphiphilic resin-supported palladium catalyst for high-throughput cross-coupling in water
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(figure presented) The Suzuki-Miyaura coupling of aryl halides (8 varieties) and aryl-or vinylboronic acids (12 varieties) took place in water in the presence of a palladium complex of an amphiphilic polystyrene-poly(ethylene glycol) copolymer resin-supported N-anchored 2-aza-1,3-bis(diphenylphosphino)-propane ligand and potassium carbonate to give uniform and quantitative yields of the corresponding biaryls (96 varieties).
- Uozumi, Yasuhiro,Nakai, Yasushi
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p. 2997 - 3000
(2007/10/03)
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- Palladium- or Nickel-Catalyzed Cross-Coupling of Organic Reagents with Aryl Triflates and Halides
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The reaction of organotitanium reagents, methyltitanium triisopropoxide [MeTi(i-PrO)3] and phenyltitanium triisopropoxide [PhTi(i-PrO)3], with aryl triflates and halides proceeded in the presence of 1.0 percent of palladium catalyst coordinated with (R*)-N,N-dimethyl-1-[(S*)-2-(diphenylphosphino)ferrocenyl]ethylamine [(R*)-(S*)-PPFA] in refluxing THF to give a quantitative yield of the corresponding cross-coupling products.
- Han, Jin Wook,Tokunaga, Norihito,Hayashi, Tamio
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p. 871 - 874
(2007/10/03)
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