- Ruthenium-Catalyzed C-H Arylation and Alkenylation of Furfural Imines with Boronates
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A Ru0-catalyzed direct C-H arylation and alkenylation of furfural imines with aryl- or alkenyl-boronates, in the presence of benzylideneacetone as a sacrificial hydride acceptor, is disclosed. This reaction provides access, after hydrolysis, to C3-arylated or vinylated furfural derivatives, and thus valorizes these relevant building-blocks obtained from lignocellulosic biomass. This approach, involving C-H activation by a Ru0/RuII, cycle offers several advantages, notably simple, mild and neutral reaction conditions.
- Siopa, Filipa,Ramis Cladera, Valérie-Anne,Afonso, Carlos Alberto Mateus,Oble, Julie,Poli, Giovanni
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supporting information
p. 6101 - 6106
(2018/09/18)
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- Rhodium-Catalyzed Arylative Transformations of Propargylic Diols: Dual Role of the Rhodium Catalyst
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Controllable synthesis of a variety of allenic alcohols and 2,5-dihydrofurans by rhodium(I)-catalyzed arylative transformations of propargylic diols is reported. The hydroxorhodium catalyst was found to play dual role: it catalyzed the arylation/dehydroxylation reaction of propargylic diols to afford allenic alcohols, and besides, it could convert to a cationic rhodium species in situ, which catalyzed the intramolecular hydroalkoxylation of allenic alcohols to form dihydrofurans. Remarkably, generation of the cationic rhodium species is dependent on the arylboron reagent used. Thus, the controllable synthesis is achieved by simply changing the arylboron reagent. (Figure presented.).
- Xing, Junhao,Zhu, Yong,Lin, Xiao,Liu, Na,Shen, Yue,Lu, Tao,Dou, Xiaowei
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supporting information
p. 1595 - 1599
(2018/03/01)
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- Selective Monoarylation of Aromatic Ketones and Esters via Cleavage of Aromatic Carbon-Heteroatom Bonds by Trialkylphosphine Ruthenium Catalysts
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We report here the ruthenium-catalyzed selective monoarylation of aromatic ketones bearing two ortho carbon-heteroatom (O or N) bonds. Under the newly developed catalyst system consisting of RuHCl(CO)(PiPr3)2, CsF, and sty
- Kondo, Hikaru,Kochi, Takuya,Kakiuchi, Fumitoshi
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supporting information
p. 794 - 797
(2017/03/01)
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- The drastic effect of cobalt and chromium catalysts in the borylation of arylzinc reagents
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A new synthetic approach to arylboronic esters from arylzinc reagents with boryl electrophiles MeOB(OR)2 has been developed. Furthermore, this protocol could be applied to the cyclization/borylation of alkynylaryl iodides to afford cyclized vinylboronic esters.
- Komeyama, Kimihiro,Kiguchi, Shinnosuke,Takaki, Ken
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supporting information
p. 7009 - 7012
(2016/06/09)
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- Beyond Directed ortho Metalation: Ruthenium-Catalyzed Amide-Directed CAr-OMe Activation/Cross-Coupling Reaction of Naphthamides with Aryl Boronates
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A new and general synthetic methodology for the construction of biaryl, heterobiaryl, and polyaryl molecules by the ruthenium-catalyzed cross-coupling of ortho-methoxy naphthamides with aryl boroneopentylates is described. The isomeric 1-MeO-2-naphthamides and 2-MeO-1-naphthamides furnish an expansive series of arylated naphthamides in excellent yields. Competition experiments showed the higher reactivity of 1-MeO-2-naphthamide over 2-MeO-benzamide. Orthogonality between the C-O activation/cross-coupling and the Suzuki-Miyaura reactions was established. The method provides naphthalenes which are difficult to prepare by directed ortho metalation.
- Zhao, Yigang,Snieckus, Victor
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supporting information
p. 4674 - 4677
(2015/10/12)
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- C-H activation by amide chelation control: Ruthenium-catalyzed direct synthesis of 2-Aryl-3-furanamides
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A new, catalytic methodology for the synthesis of heterobiaryls by the ruthenium-catalyzed C-H activation/cross-coupling of heterocyclic amides with aryl boroneopentylates is surveyed. From this survey, the highly regioselective reaction of furan-3-carboxamide to give 2-aryl-3-furanamides is optimized and generalized in scope with respect to the aryl boroneopentylate coupling partners. Established thereby is a one-step synthetic method which may supercede the broadly applied two-step directed ortho metalation (DoM)-cross coupling reaction involving cryogenic and strong base conditions and which has potential for further ortho and remote metalation chemistry.
- Zhao, Yigang,Snieckus, Victor
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supporting information
p. 1527 - 1532
(2014/06/09)
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- Beyond directed ortho metalation: Ruthenium-catalyzed amide-directed C Ar-N activation/C-C coupling reaction of anthranilamides with organoboronates
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A new, catalytic, and general methodology for the synthesis of biaryls and heterobiaryls by the cross coupling of anthranilamide derivatives (o-NMe 2 benzamides) with aryl boroneopentylates is described. The reaction proceeds under catalytic RuH2(CO)(PPh3)3 conditions driven by the activation of the unreactive C-N bond by amide directing group (DG)-Ru catalyst chelation. High regioselectivity, orthogonality with the Suzuki-Miyaura reaction, operational simplicity, and convenient scale-up are features of these reactions which may lend themselves to industrial applications.
- Zhao, Yigang,Snieckus, Victor
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supporting information
p. 3200 - 3203
(2014/07/08)
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- Beyond directed ortho metalation: Ru-catalyzed CAr-O activation/cross-coupling reaction by amide chelation
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Disclosed is a new, catalytic, and general methodology for the chemical synthesis of biaryl, heterobiaryl, and polyaryl molecules by the cross-coupling of o-methoxybenzamides with aryl boroneopentylates. The reaction is based on the activation of the unreactive C-OMe bond by the proximate amide directing group using catalytic RuH2(CO)(PPh3)3 conditions. A one-step, base-free coupling process is thereby established that has the potential to supersede the useful two-step directed ortho metalation/cross- coupling reaction involving cryogenic temperature and strong base conditions. High regioselectivity, orthogonality with the Suzuki-Miyaura reaction, operational simplicity, minimum waste, and convenient scale-up make these reactions suitable for industrial applications.
- Zhao, Yigang,Snieckus, Victor
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supporting information
p. 11224 - 11227
(2014/09/29)
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- Nickel-catalysed carboxylation of organoboronates
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A nickel/N-heterocyclic carbene (NHC) catalysed carboxylation of aryl-, heteroaryl- and alkenylboronates, affording the corresponding carboxylic acids, has been developed. This transformation proceeds under one atmosphere of CO 2 with a broad range of substrates and exhibits good functional group compatibility. the Partner Organisations 2014.
- Makida, Yusuke,Marelli, Enrico,Slawin, Alexandra M. Z.,Nolan, Steven P.
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supporting information
p. 8010 - 8013
(2014/07/08)
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- Nickel-catalyzed borylation of halides and pseudohalides with tetrahydroxydiboron [B2(OH)4]
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Arylboronic acids are gaining increased importance as reagents and target structures in a variety of useful applications. Recently, the palladium-catalyzed synthesis of arylboronic acids employing the atom-economical tetrahydroxydiboron (BBA) reagent has been reported. The high cost associated with palladium, combined with several limitations of both palladium- and copper-catalyzed processes, prompted us to develop an alternative method. Thus, the nickel-catalyzed borylation of aryl and heteroaryl halides and pseudohalides using tetrahydroxydiboron (BBA) has been formulated. The reaction proved to be widely functional group tolerant and applicable to a number of heterocyclic systems. To the best of our knowledge, the examples presented here represent the only effective Ni-catalyzed Miyaura borylations conducted at room temperature.
- Molander, Gary A.,Cavalcanti, Livia N.,Garcia-Garcia, Carolina
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p. 6427 - 6439
(2013/07/26)
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- Copper-catalyzed amination of arylboronates with N,N-dialkylhydroxylamines
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A tolerant coupling: The title reaction has been developed to deliver arylamines (see scheme; Bz=benzoyl, dppbz=1,2-bis(diphenylphosphino)benzene). The catalysis is based on electrophilic, umpolung amination and enables the use of secondary acyclic amines. Various functional groups are tolerated, thus opening up a new substrate class for the Chan-Lam-type coupling.
- Matsuda, Naoki,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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supporting information; body text
p. 3642 - 3645
(2012/05/20)
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- Ni(COD)2/PCy3 catalyzed cross-coupling of aryl and heteroaryl neopentylglycolboronates with aryl and heteroaryl mesylates and sulfamates in THF at room temperature
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Reaction conditions for the Ni(COD)2/PCy3 catalyzed cross-coupling of aryl neopentylglycolboronates with aryl mesylates were developed. By using optimized reaction conditions, Ni(COD)2/PCy 3 was shown to be a versatile catalyst for the cross-coupling of a diversity of aryl neopentylglycolboronates with aryl and heteroaryl mesylates and sulfamates containing both electron-donating and electron-withdrawing substituents in their para, ortho, and meta positions in THF at room temperature. This Ni-catalyzed cross-coupling of aryl neopentylglycolboronates is also effective for the synthesis of heterobiaryls and biaryls containing electrophilic functionalities sensitive to organolithium and organomagnesium derivatives. In combination with the recently developed Nicatalyzed neopentylglycolborylation, all Ni-catalyzed routes to functional biaryls and heterobiaryls are now easily accessible (Figure presented).
- Leowanawat, Pawaret,Zhang, Na,Resmerita, Ana-Maria,Rosen, Brad M.,Percec, Virgil
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experimental part
p. 9946 - 9955
(2012/01/15)
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- Copper-catalyzed cross-coupling reaction of organoboron compounds with primary alkyl halides and pseudohalides
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Non-activated alkyl electrophiles, including alkyl iodides, bromides, tosylates, mesylates, and even chlorides, underwent copper-catalyzed cross-coupling with aryl boron compounds and alkyl 9-BBN reagents (see scheme; 9-BBN=9-borabicyclo[3.3.1]nonane). The reactions proceed with practically useful reactivities and thus complement palladium- and nickel-catalyzed Suzuki-Miyaura coupling reactions of alkyl halides.
- Yang, Chu-Ting,Zhang, Zhen-Qi,Liu, Yu-Chen,Liu, Lei
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supporting information; experimental part
p. 3904 - 3907
(2011/05/15)
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- Ruthenium-catalyzed carbon-carbon bond formation via the cleavage of an unreactive aryl carbon-nitrogen bond in aniline derivatives with organoboronates
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The RuH2(CO)(PPh3)3-catalyzed reaction of 2-amino-6-methylacetophenone with phenylboronic acid 2,2-dimethyl-1,3-propanediol ester in refluxing toluene gave the corresponding phenylation product in 83% yield via aryl carbon
- Ueno, Satoshi,Chatani, Naoto,Kakiuchi, Fumitoshi
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p. 6098 - 6099
(2008/02/08)
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