- Neopentylglycolborylation of aryl mesylates and tosylates catalyzed by Ni-based mixed-ligand systems activated with Zn
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(Chemical Presented) The mixed-ligand system NiCl2(dppp)/dppf is shown to be an effective catalyst for the neopentylglycolborylation of ortho-, meta-, and para-substituted electron-rich and electrondeficient aryl mesylates and tosylates. The ad
- Wilson, Daniela A.,Wilson, Christopher J.,Moldoveanu, Costel,Resmerita, Ana-Maria,Corcoran, Patrick,Hoang, Lisa M.,Rosen, Brad M.,Percec, Virgil
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- Palladium-catalyzed aerobic oxidative carbonylation of arylboronate esters under mild conditions
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(Figure Presented) "CO"n Air: The title reaction was carried out using [PdCl2(PPh3)2 ] as the catalyst precursor under very mild conditions (balloon pressure of CO and air, at 40- 50°C), and produced a wide range of aryl carboxyl esters 2 in good to excellent yields. Remarkable selectivity between oxidative carbonylation and homocoupling of arylboronate esters l was also achieved.
- Liu, Qiang,Li, Gang,He, Jun,Liu, Jing,Li, Peng,Lei, Aiwen
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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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- Nickel-Catalyzed Decarbonylative Borylation of Amides: Evidence for Acyl C?N Bond Activation
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A nickel/N-heterocyclic carbene catalytic system has been established for decarbonylative borylation of amides with B2nep2by C?N bond activation. This transformation shows good functional-group compatibility and can serve as a powerful synthetic tool for late-stage borylation of amide groups in complex compounds. More importantly, as a key intermediate, the structure of an acyl nickel complex was first confirmed by X-ray analysis. Furthermore, the decarbonylative process was also observed. These findings confirm the key mechanistic features of the acyl C?N bond activation process.
- Hu, Jiefeng,Zhao, Yue,Liu, Jingjing,Zhang, Yemin,Shi, Zhuangzhi
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- Nickel-Catalyzed Decarbonylative Borylation and Silylation of Esters
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The nickel-catalyzed direct borylation and silylation of phenolic esters has been established. The key to this highly efficient acyl C-O bond borylative and silylative cleavage depends on the appropriate choice of different ligands and additives in the pr
- Pu, Xinghui,Hu, Jiefeng,Zhao, Yue,Shi, Zhuangzhi
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- Cobalt-Catalyzed C(sp2)-C(sp3) Suzuki-Miyaura Cross Coupling
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A cobalt-catalyzed method for the C(sp2)-C(sp3) Suzuki-Miyaura cross coupling of aryl boronic esters and alkyl bromides is described. Cobalt-ligand combinations were assayed with high-throughput experimentation, and cobalt(II) sources with trans-N,N′-dimethylcyclohexane-1,2-diamine (DMCyDA, L1) produced optimal yield and selectivity. The scope of this transformation encompassed steric and electronic diversity on the aryl boronate nucleophile as well as various levels of branching and synthetically valuable functionality on the electrophile. Radical trap experiments support the formation of electrophile-derived radicals during catalysis.
- Ludwig, Jacob R.,Simmons, Eric M.,Wisniewski, Steven R.,Chirik, Paul J.
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supporting information
(2020/11/02)
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- Transition-Metal-Free ipso-Trifluoromethylthiolation of Lithium Aryl Boronates
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A transition-metal-free direct trifluoromethylthiolation of the ipso-carbon of lithium aryl boronates with trifluoromethanesulfenate under mild conditions was described. In addition, late-stage site-selective C-H borylation/trifluoromethylation and C-Cl b
- Shen, Feng,Zheng, Hanliang,Xue, Xiao-Song,Lu, Long,Shen, Qilong
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supporting information
p. 6347 - 6351
(2019/08/20)
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- Cu-Catalyzed cross-coupling reactions of epoxides with organoboron compounds
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A copper-catalyzed cross-coupling reaction of epoxides with arylboronates is described. This reaction is not limited to aromatic epoxides, because aliphatic epoxides are also suitable substrates. In addition, N-sulfonyl aziridines can be successfully converted into the products. This reaction provides convenient access to β-phenethyl alcohols, which are valuable synthetic intermediates.
- Lu, Xiao-Yu,Yang, Chu-Ting,Liu, Jing-Hui,Zhang, Zheng-Qi,Lu, Xi,Lou, Xin,Xiao, Bin,Fu, Yao
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supporting information
p. 2388 - 2391
(2015/02/05)
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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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- Cu-Catalyzed Suzuki-Miyaura reactions of primary and secondary benzyl halides with arylboronates
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A copper-catalyzed Suzuki-Miyaura coupling of benzyl halides with arylboronates is described. Varieties of primary benzyl halides as well as more challenging secondary benzyl halides with β hydrogens or steric hindrance could be successfully converted into the corresponding products. Thus it provides access to diarylmethanes, diarylethanes and triarylmethanes. This journal is the Partner Organisations 2014.
- Sun, Yan-Yan,Yi, Jun,Lu, Xi,Zhang, Zhen-Qi,Xiao, Bin,Fu, Yao
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supporting information
p. 11060 - 11062
(2014/09/30)
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- PROCESS FOR THE BORYLATION OF ORGANOHALIDES
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The present invention relates to a process for the borylation of organohalides.
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Page/Page column 11; 12; 13
(2013/03/26)
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- Ruthenium-catalyzed α-(hetero)arylation of saturated cyclic amines: Reaction scope and mechanism
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Transition-metal-catalyzed sp3 C-H activation has emerged as a powerful approach to functionalize saturated cyclic amines. Our group recently disclosed a direct catalytic arylation reaction of piperidines at the α position to the nitrogen atom. 1-(Pyridin-2-yl)piperidine could be smoothly α-arylated if treated with an arylboronic ester in the presence of a catalytic amount of [Ru3(CO)12] and one equivalent of 3-ethyl-3-pentanol. A systematic study on the substrate and reagent scope of this transformation is disclosed in this paper. The effect of substitution on both the piperidine ring and the arylboronic ester has been investigated. Smaller (pyrrolidine) and larger (azepane) saturated ring systems, as well as benzoannulated derivatives, were found to be compatible substrates with the α-arylation protocol. The successful use of a variety of heteroarylboronic esters as coupling partners further proved the power of this direct functionalization method. Mechanistic studies have allowed for a better understanding of the catalytic cycle of this remarkable transformation featuring an unprecedented direct transmetalation on a RuII-H species. Copyright
- Peschiulli, Aldo,Smout, Veerle,Storr, Thomas E.,Mitchell, Emily A.,Elias, Zdenek,Herrebout, Wouter,Berthelot, Didier,Meerpoel, Lieven,Maes, Bert U. W.
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supporting information
p. 10378 - 10387
(2013/09/02)
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- Borylation of organo halides and triflates using tetrakis(dimethylamino) diboron
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We report a new in situ borylation method using tetrakis(dimethylamino) diboron, DMA4B2, in the presence of a diol. Our method uses standard borylation conditions and readily available Pd-catalysts. The scope of this method includes aryl halides and triflates as well as vinyl halides and triflates. The method successfully works with a broad range of diols, enabling the selection of the best boronic ester for subsequent Suzuki coupling.
- Bello, Charles S.,Schmidt-Leithoff, Joachim
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p. 6230 - 6235,6
(2012/12/11)
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- Rhodium(I)-catalyzed borylation of nitriles through the cleavage of carbon-cyano bonds
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The reaction of aryl cyanides with diboron in the presence of a rhodium/Xantphos catalyst and DABCO affords arylboronic esters via carbon-cyano bond cleavage. This unprecedented mode of reactivity for a borylrhodium species allows the regioselective intro
- Tobisu, Mamoru,Kinuta, Hirotaka,Kita, Yusuke,Remond, Emmanuelle,Chatani, Naoto
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p. 115 - 118
(2012/03/07)
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- Controlled alcohol-carbonyl interconversion by nickel catalysis
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All in one pot: A general synthetic platform allows the interconversion of alcohols and carbonyl compounds in a predictable and controlled fashion in one pot. Under the action of a Ni catalyst, PhCl, CsF, and arylboronates, several multistep alcohol-carbonyl interconversions have been achieved with good overall efficiency (see scheme). A one-pot nickel-catalyzed synthesis of flumecinol (a hepatic microsomal enzyme inducer) has also been demonstrated. Copyright
- Maekawa, Takehisa,Sekizawa, Hiromi,Itami, Kenichiro
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supporting information; experimental part
p. 7022 - 7026
(2011/09/30)
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