- Catalyst activation, deactivation, and degradation in palladium-mediated negishi cross-coupling reactions
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Pd-mediated Negishi cross-coupling reactions were studied by a combination of kinetic measurements, electrospray-ionization (ESI) mass spectrometry, 31P NMR and UV/Vis spectroscopy. The kinetic measurements point to a rate-determining oxidative addition. Surprisingly, this step seems to involve not only the Pd catalyst and the aryl halide substrate, but also the organozinc reagent. In this context, the ESI-mass spectrometric observation of heterobimetallic Pd-Zn complexes [L2PdZnR]+ (L=S-PHOS, R=Bu, Ph, Bn) is particularly revealing. The inferred presence of these and related neutral complexes with a direct Pd-Zn interaction in solution explains how the organozinc reagent can modulate the reactivity of the Pd catalyst. Previous theoretical calculations by Gonzlez-Prez et al. (Organometallics 2012, 31, 2053) suggest that the complexation by the organozinc reagent lowers the activity of the Pd catalyst. Presumably, a similar effect also causes the rate decrease observed upon addition of ZnBr2. In contrast, added LiBr apparently counteracts the formation of Pd-Zn complexes and restores the high activity of the Pd catalyst. At longer reaction times, deactivation processes due to degradation of the S-PHOS ligand and aggregation of the Pd catalyst come into play, thus further contributing to the appreciable complexity of the title reaction. Catalytic complexity: The Pd catalyst used in Negishi cross-coupling reactions shows an unexpected heterogeneity and complexity. Among the various species observed in solution, heterobimetallic Pd-Zn complexes are of particular interest (see figure). These species also seem key to understanding the kinetics of Negishi cross-coupling reactions. S-PHOS=2-dicyclohexylphosphino-2,6-dimethoxybiphenyl.
- B?ck, Katharina,Feil, Julia E.,Karaghiosoff, Konstantin,Koszinowski, Konrad
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Read Online
- Photo-Ni-Dual-Catalytic C(sp2)-C(sp3) Cross-Coupling Reactions with Mesoporous Graphitic Carbon Nitride as a Heterogeneous Organic Semiconductor Photocatalyst
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The synergistic combination of a heterogeneous organic semiconductor mesoporous graphitic carbon nitride (mpg-CN) and a homogeneous nickel catalyst with visible-light irradiation at room temperature affords the C(sp2)-C(sp3) cross-co
- Antonietti, Markus,Ghosh, Indrajit,K?nig, Burkhard,Khamrai, Jagadish,Savateev, Aleksandr
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p. 3526 - 3532
(2020/04/09)
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- Construction of Di(hetero)arylmethanes Through Pd-Catalyzed Direct Dehydroxylative Cross-Coupling of Benzylic Alcohols and Aryl Boronic Acids Mediated by Sulfuryl Fluoride (SO2F2)
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A practical Pd-catalyzed direct dehydroxylative coupling of (hetero)benzylic alcohols with (hetero)arylboronic acids for the constructions of di(hetero)arylmethane derivatives under SO2F2 was described. This new method provided a strategically distinct approach to di(hetero)arylmethane derivatives from readily available and abundant benzylic alcohols under mild condition.
- Zhao, Chuang,Zha, Gao-Feng,Fang, Wan-Yin,Rakesh,Qin, Hua-Li
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p. 1801 - 1807
(2019/02/07)
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- Super electron donor-mediated reductive desulfurization reactions
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The desulfurization of thioacetals and thioethers by a pyridine-derived electron donor is described. This methodology provides efficient access to the reduced products in high yields and does not require the use of transition-metals, elemental alkali-metals, or hydrogen atom donors.
- Nozawa-Kumada, Kanako,Ito, Shungo,Noguchi, Koto,Shigeno, Masanori,Kondo, Yoshinori
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p. 12968 - 12971
(2019/11/05)
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- Cobalt-Catalyzed Formation of Functionalized Diarylmethanes from Benzylmesylates and Aryl Halides
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A simple cobalt-catalyzed reductive coupling protocol allowing the synthesis of functionalized diarylmethanes from benzyl mesylate is described. The possibility to directly use the benzyl alcohol as a result of a two-step reaction is also presented. This method tolerates a variety of functional groups. A benzyl radical is likely involved. (Figure presented.).
- Reddy, Bhoomireddy Rajendra Prasad,Chowdhury, Sushobhan,Auffrant, Audrey,Gosmini, Corinne
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p. 3026 - 3029
(2018/08/24)
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- Mechanochemical Activation of Zinc and Application to Negishi Cross-Coupling
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A form independent activation of zinc, concomitant generation of organozinc species and engagement in a Negishi cross-coupling reaction via mechanochemical methods is reported. The reported method exhibits a broad substrate scope for both C(sp3)–C(sp2) and C(sp2)–C(sp2) couplings and is tolerant to many important functional groups. The method may offer broad reaching opportunities for the in situ generation organometallic compounds from base metals and their concomitant engagement in synthetic reactions via mechanochemical methods.
- Cao, Qun,Howard, Joseph L.,Wheatley, Emilie,Browne, Duncan L.
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p. 11339 - 11343
(2018/08/28)
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- Visible-Light-Induced Nickel-Catalyzed Negishi Cross-Couplings by Exogenous-Photosensitizer-Free Photocatalysis
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The merging of photoredox and transition-metal catalysis has become one of the most attractive approaches for carbon–carbon bond formation. Such reactions require the use of two organo-transition-metal species, one of which acts as a photosensitizer and t
- Abdiaj, Irini,Fontana, Alberto,Gomez, M. Victoria,de la Hoz, Antonio,Alcázar, Jesús
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supporting information
p. 8473 - 8477
(2018/04/30)
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- Expanding the limit of Pd-catalyzed decarboxylative benzylations
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The Pd-catalyzed decarboxylative cross-coupling of electron-deficient aryl acetates with aryl bromides is reported. The method widens the scope of benzylic partners that can undergo efficient reactivity from highly activated nitrophenylacetates established previously, to a diverse series of substrates bearing modestly stabilizing groups, allowing direct access to functionalized diarylmethanes. Mechanistic studies support the role of dienolates as key intermediates in the coupling process.
- Kong, Duanyang,Moon, Patrick J.,Qian, Wenyu,Lundgren, Rylan J.
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supporting information
p. 6835 - 6838
(2018/06/26)
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- Transition-Metal-Free Suzuki-Type Cross-Coupling Reaction of Benzyl Halides and Boronic Acids via 1,2-Metalate Shift
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Cross-coupling of organoboron compounds with electrophiles (Suzuki-Miyaura reaction) has greatly advanced C-C bond formation and has been well received in medicinal chemistry. During the past 50 years, transition metals have played a central role throughout the catalytic cycle of this important transformation. In this process, chemoselectivity among multiple carbon-halogen bonds is a common challenge. In particular, selective oxidative addition of transition metals to alkyl halides rather than aryl halides is difficult due to unfavorable transition states and bond strengths. We describe a new approach that uses a single organic sulfide catalyst to activate both C(sp3) halides and arylboronic acids via a zwitterionic boron "ate" intermediate. This "ate" species undergoes a 1,2-metalate shift to afford Suzuki coupling products using benzyl chlorides and arylboronic acids. Various diaryl methane analogues can be prepared, including those with complex and biologically active motifs. The reactions proceed under transition-metal-free conditions, and C(sp2) halides, including aryl bromides and iodides, are unaffected. The orthogonal chemoselectivity is demonstrated in the streamlined synthesis of highly functionalized diaryl methane scaffolds using multi-halogenated substrates. Preliminary mechanistic experiments suggest both the sulfonium salt and the sulfur ylide are involved in the reaction, with the formation of sulfonium salt being the slowest step in the overall catalytic cycle.
- He, Zhiqi,Song, Feifei,Sun, Huan,Huang, Yong
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supporting information
p. 2693 - 2699
(2018/02/28)
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- Radical-Based C?C Bond-Forming Processes Enabled by the Photoexcitation of 4-Alkyl-1,4-dihydropyridines
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We report herein that 4-alkyl-1,4-dihydropyridines (alkyl-DHPs) can directly reach an electronically excited state upon light absorption and trigger the generation of C(sp3)-centered radicals without the need for an external photocatalyst. Selective excitation with a violet-light-emitting diode turns alkyl-DHPs into strong reducing agents that can activate reagents through single-electron transfer manifolds while undergoing homolytic cleavage to generate radicals. We used this photochemical dual-reactivity profile to trigger radical-based carbon–carbon bond-forming processes, including nickel-catalyzed cross-coupling reactions.
- Buzzetti, Luca,Prieto, Alexis,Roy, Sudipta Raha,Melchiorre, Paolo
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supporting information
p. 15039 - 15043
(2017/11/20)
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- One-pot borylation/Suzuki-Miyaura sp2-sp3 cross-coupling
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We describe the first one-pot borylation/Suzuki-Miyaura sp2-sp3 cross-coupling between readily available aryl (pseudo)halides and activated alkyl chlorides. This method streamlines the synthesis of diaryl methanes, α-aryl carbonyls and allyl aryl compounds, substructures that are commonly found in life changing drug molecules.
- Whitaker, Luke,Harb, Hassan Y.,Pulis, Alexander P.
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p. 9364 - 9367
(2017/08/23)
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- Nickel-Catalyzed Cross-Coupling of Functionalized Organo manganese Reagents with Aryl and Heteroaryl Halides Promoted by 4-Fluorostyrene
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A catalytic system consisting of Ni(acac) 2 (5 mol%) and 4-fluorostyrene (20 mol%) allows a convenient cross-coupling of functionalized organomanganese reagents with a variety of aryl and heteroaryl halides leading to polyfunctionalized diaryl- and arylheteroarylmethane derivatives.
- Benischke, Andreas D.,Desaintjean, Alexandre,Juli, Thomas,Cahiez, Gérard,Knochel, Paul
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p. 5396 - 5412
(2017/12/14)
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- Versatile C(sp2)?C(sp3) Ligand Couplings of Sulfoxides for the Enantioselective Synthesis of Diarylalkanes
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The reaction of chiral (hetero)aryl benzyl sulfoxides with Grignard reagents affords enantiomerically pure diarylalkanes in up to 98 % yield and greater than 99.5 % enantiomeric excess. This ligand coupling reaction is tolerant to multiple substitution patterns and provides access to diverse areas of chemical space in three operationally simple steps from commercially available reagents. This strategy provides orthogonal access to electron-deficient heteroaromatic compounds, which are traditionally synthesized by transition metal catalyzed cross-couplings, and circumvents common issues associated with proto-demetalation and β-hydride elimination.
- Dean, William M.,?iau?iulis, Mindaugas,Storr, Thomas E.,Lewis, William,Stockman, Robert A.
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p. 10013 - 10016
(2016/08/16)
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- Cobalt-Catalyzed Reductive Cross-Coupling Between Benzyl Chlorides and Aryl Halides
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A new protocol for the direct reductive cobalt-catalyzed arylation of benzyl chlorides has been developed in order to form functionalized diarylmethanes. A variety of reactive groups either on the aryl or the benzyl halide was employed. This represents the first cobalt-catalyzed reductive cross-coupling which does not require any ligand and pyridine. A reaction pathway is proposed involving a radical benzyl species. (Figure presented.).
- Pal, Suman,Chowdhury, Sushobhan,Rozwadowski, Elodie,Auffrant, Audrey,Gosmini, Corinne
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supporting information
p. 2431 - 2435
(2016/08/16)
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- Iron-Catalyzed Cross-Coupling of Benzylic Manganese Chlorides with Aryl and Heteroaryl Halides
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The use of FeCl2 (10 mol%) allows a convenient iron-catalyzed cross-coupling reaction of benzylic manganese(II) chlorides with various aryl and heteroaryl chlorides, bromides and iodides leading to polyfunctionalized diaryl- and arylheteroarylmethane derivatives.
- Benischke, Andreas D.,Breuillac, Antoine J. A.,Moyeux, Alban,Cahiez, Gérard,Knochel, Paul
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p. 471 - 476
(2016/02/09)
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- N-heterocyclic carbene-palladium(II)-1-methylimidazole complex-catalyzed Suzuki-Miyaura coupling of benzyl sulfonates with arylboronic acids
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The first example of palladium-catalyzed Suzuki-Miyaura coupling between benzyl sulfonates and arylboronic acids was reported in this paper. In the presence of a well-defined, air-stable and easily available NHC-Pd(ii)-Im complex, all reactions worked well to give the desired products in good to almost quantitative yields under the optimal conditions. Electron-rich, -neutral, -poor and sterically-hindered substituents on both substrates are tolerated in such transformation, providing a convenient, efficient and alternative method for the synthesis of diarylmethanes.
- Wang, Xiao-Xia,Xu, Bin-Bin,Song, Wen-Ting,Sun, Kai-Xin,Lu, Jian-Mei
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p. 4925 - 4930
(2015/05/05)
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- Visible light photoredox-catalyzed deoxygenation of alcohols
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Carbon-oxygen single bonds are ubiquitous in natural products whereas efficient methods for their reductive defunctionalization are rare. In this work an environmentally benign protocol for the activation of carbon-oxygen single bonds of alcohols towards a reductive bond cleavage under visible light photocatalysis was developed. Alcohols were activated as 3,5-bis(trifluoromethyl)-substituted benzoates and irradiation with blue light in the presence of [Ir(ppy)2( dtb-bpy)](PF6 ) as visible light photocatalyst and Hünig's base as sacrificial electron donor in an acetonitrile/water mixture generally gave good to excellent yields of the desired defunctionalized compounds. Functional group tolerance is high but the protocol developed is limited to benzylic, α-carbonyl, and α-cyanoalcohols; with other alcohols a slow partial C-F bond reduction in the 3,5-bis(trifluoromethyl)benzoate moiety occurs.
- Rackl, Daniel,Kais, Viktor,Kreitmeier, Peter,Reiser, Oliver
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p. 2157 - 2165
(2015/01/09)
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- Cucurbit[7]uril promoting PdCl2-catalyzed cross-coupling reaction of benzyl halides and arylboronic acids in aqueous media
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The research provides a novel approach for producing diarylmethane derivatives using CB[7]-NaCl-PdCl2catalyzed Suzuki cross-coupling reaction of benzyl chloride derivatives and arylboronic acids in ethanol aqueous solution.
- Zhao, Guangkuan,Wang, Zhen,Wang, Ruixin,Li, Jingya,Zou, Dapeng,Wu, Yangjie
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supporting information
p. 5319 - 5322
(2015/01/16)
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- Synthesis of Ni(II) complexes with unsymmetric [O,N,O′]-pincer ligands and their use as precatalysts in carbon-carbon bond formations to access diarylmethanes
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1-Acetyl-[1a,3,5-CF3,1-C(=O)CH3] and 1-benzoyl-5-hydroxypyrazolines [1b, 3,5-CF3, 1-C(=O)C 6H5] have been synthesized and reacted with Ni(OAc) 2·4H2O in the presence of PPh3 to form square planar nickel complexes, which revealed a O,N,O′-coordination. An additional coordination site on the nickel center is occupied by one triphenylphosphane ligand. After having investigated the properties of the complexes, catalytic experiments have been carried out to synthesize diarylmethanes. Applying the complexes in the nickel-catalyzed carbon-carbon cross coupling of aryl halides with benzylzinc bromide excellent yields and selectivities of the corresponding diarylmethane have been obtained. Moreover, various experiments have been performed to shed light on the underlying reaction mechanism.
- Someya, Chika I.,Irran, Elisabeth,Enthaler, Stephan
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p. 136 - 144
(2014/07/08)
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- Pd-catalyzed chemoselective threefold cross-coupling of triarylbismuths with benzylic bromides
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An efficient palladium-catalyzed protocol was demonstrated for the chemoselective cross-coupling of functionalized benzylic bromides with triarylbismuth reagents. Under the established conditions, catalyzed by palladium in the presence of K3PO
- Rao, Maddali L. N.,Dhanorkar, Ritesh J.
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p. 6794 - 6798
(2013/05/23)
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- Preparation of functionalized organoindium reagents by means of magnesium insertion into organic halides in the presence of InCl3 at room temperature
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Magnesium, indium, palladium: An efficient one-pot procedure for the direct preparation of triorganoindium reagents from organic halides by means of magnesium insertion in the presence of InCl3 and LiCl is reported (see scheme). The organoindium reagents are obtained in good yields from functionalized aryl, heteroaryl, and alkyl bromides and benzyl chlorides at 25 °C in THF within 4h. Moreover, the resulting organoindium reagents could be efficiently used as reagents in Pd-catalyzed cross-coupling reactions with a wide functional group tolerance. Copyright
- Bernhardt, Sebastian,Shen, Zhi-Liang,Knochel, Paul
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supporting information
p. 828 - 833
(2013/02/23)
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- Nickel-catalyzed cross-coupling of aryltrimethylammonium iodides with organozinc reagents
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Broad scope and good tolerance: An efficient cross-coupling of aryltrimethylammonium iodide salts with aryl-, methyl-, and benzylzinc chlorides catalyzed by [Ni(PCy3)2Cl2] has been achieved (see scheme). The reaction involves cleavage of the C-N bond and displays broad substrate scope and good functional group tolerance. NMP=N-methylpyrrolidine. Copyright
- Xie, Lan-Gui,Wang, Zhong-Xia
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supporting information; experimental part
p. 4901 - 4904
(2011/06/22)
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- Cross-couplings between benzylic and aryl halides on water : Synthesis of diarylmethanes
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A remarkably simple entry to unsymmetrical diarylmethanes has been developed that relies on an in situ organozinc-mediated, palladium-catalyzed cross-coupling. Thus, by mixing a benzyl and aryl halide together in the presence of Zn metal and a Pd catalyst, diarylmethanes are formed at room temperature without assistance by a surfactant; hence, on water .
- Duplais, Christophe,Krasovskiy, Arkady,Wattenberg, Alina,Lipshutz, Bruce H.
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supporting information; experimental part
p. 562 - 564
(2010/05/01)
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- Direct method for carbon-carbon bond formation: The functional group tolerant cobalt-catalyzed alkylation of aryl halides
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(Figure Presented). A new protocol for the direct cobaltcatalyzed alkylation of aryl halides has been developed that proceeds smoothly in the presence of phosphanes or bipyridines as ligands with a variety of alkyl halides, including challenging alkyl electrophiles bearing β hydrogen atoms (see scheme). Sensitive functional groups are tolerated on both coupling partners, thus, significantly extending the general scope of transition-metal-catalyzed alkylation of aryl halides.
- Amatore, Muriel,Gosmini, Corinne
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supporting information; experimental part
p. 5848 - 5852
(2010/09/03)
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- Synthesis of functionalised diarylmethanes via a cobalt-catalysed cross-coupling of arylzinc species with benzyl chlorides
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A new cobalt-catalysed reductive coupling of aryl halides with benzyl chlorides is reported; a variety of diarylmethanes can be prepared in good to excellent yields under mild reaction conditions using CoBr2 as catalyst and Zn dust; this new cobalt-catalysed coupling represents a practical and interesting alternative to previously known methods for the synthesis diarylmethanes. The Royal Society of Chemistry.
- Amatore, Muriel,Gosmini, Corinne
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supporting information; experimental part
p. 5019 - 5021
(2009/06/05)
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- BIARYL SUBSTITUTED HETEROCYCLE INHIBITORS OF LTA4H FOR TREATING INFLAMMATION
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The present invention relates to a chemical genus of biaryl substituted heterocycle inhibitors of LTA4H (leukotriene A4 hydrolase) useful for the treatment and prevention and prophylaxis of inflammatory diseases and disorders. The compounds have general formula Ψ: An example is
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Page/Page column 81
(2008/06/13)
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- Synthesis of functionalized diarylmethanes via a copper-catalyzed cross-coupling of arylmagnesium reagents with benzylic phosphates
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A combination of copper chloride, triethyl phosphite, and tetrabutylammonium iodide is a very efficient catalytic system for the synthesis of polyfunctionalized diarylmethanes, using the cross-coupling reaction of arylmagnesium halides with benzylic phosphates. The antibiotic Trimethoprim has been prepared using this Cu(I)-catalyzed cross-coupling in 52% overall yield (four steps).
- Kofink, Christiane C.,Knochel, Paul
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p. 4121 - 4124
(2007/10/03)
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- Palladium-catalyzed cross-coupling of B-Benzyl-9-borabicyclo[3.3.1]nonane to furnish methylene-linked biaryls
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(Chemical Equation Presented) Benzylboranes are noticeably uncommon partners within Suzuki-Miyaura coupling reactions. B-Benzyl-9-BBN was successfully coupled to a range of aryl/heteroaryl bromides, chlorides, and triflates to give pharmacologically important methylene-linked biaryl structures. Activated, deactivated, and sterically hindered substrates were successfully coupled in high yield using Pd(PPh3)4 or Pd(OAc)2 with SPhos as the catalyst system.
- Flaherty, Alice,Trunkfield, Amy,Barton, William
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p. 4975 - 4978
(2007/10/03)
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- Direct preparation of benzylic manganese reagents from benzyl halides, sulfonates, and phosphates and their reactions: Applications in organic synthesis
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The use of highly active manganese (Mn)*, prepared by the Rieke method, was investigated for the direct preparation of benzylic manganese reagents. The oxidative addition of the highly active manganese to benzylic halides was easily completed under mild conditions. Moreover, benzylic manganese sulfonates and phosphates were prepared by direct oxidative addition of Mn* to the carbon-oxygen bonds of benzylic sulfonates and phosphates. The resulting benzylic manganese reagents were found to undergo cross-coupling reactions with a variety of electrophiles. Most of these reactions were carried out in the absence of any transition metal catalyst under mild conditions. In addition, the use of highly active manganese was also studied for preparation of homo-coupled products of functionalized benzyl halides without transition metal catalysts. These useful approaches provided not only a facile synthetic route to the preparation of resoricinolic lipids but a facile synthesis of functionalized 4-benzylpyridines by regioselective and chemo selective γ-addition of benzylic group to N-alkoxycarbonylpyridinum salts.
- Suh, YoungSung,Lee, Jun-Sik,Kim, Seoung-Hoi,Rieke, Reuben D.
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- Benzylic Manganese Halides, Sulfonates, and Phosphates: Preparation, Coupling Reactions, and Applications in Organic Synthesis
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The use of highly active manganese, prepared by the Rieke method, for the direct preparation of benzylic manganese reagents was investigated. The oxidative addition of the highly active manganese (Mn*) to benzylic halides was easily completed under mild conditions. More importantly, benzylic manganese sulfonates and phosphates were prepared by direct oxidative addition of Mn* to the carbon-oxygen bonds of benzylic sulfonates and phosphates. The resulting benzylic manganese reagents were found to undergo cross-coupling reactions with a variety of electrophiles. The majority of these reactions were carried out in the absence of any transition metal catalyst under mild conditions. This approach also provided a facile synthetic route to the preparation of resorcinolic lipids.
- Kim, Seung-Hoi,Rieke, Reuben D.
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p. 2322 - 2330
(2007/10/03)
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- Palladium catalyzed cross-couplings of organozincs in ionic liquids
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Negishi cross-coupling reactions between aryl- or benzylzinc halides and various aryl iodides smoothly occur in ionic liquids in the presence of the new ionic phosphine ligand 2. This solvent allows a facile work-up and rapid cross-coupling reactions at r
- Sirieix,Ossberger,Betzemeier,Knochel
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p. 1613 - 1615
(2007/10/03)
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- New efficient nickel- and palladium-catalyzed cross-coupling reactions mediated by tetrabutylammonium iodide
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(formula presented) The addition of Bu4NI has been found to accelerate the palladium(0)-catalyzed cross-coupling between benzylic zinc bromides and aryl or alkenyl triflates. Remarkably, it further allows a new nickel(0)-catalyzed cross-coupling between functionalized benzylic zinc reagents and primary alkyl iodides leading to polyfunctional products in good yields under mild reaction conditions (0-20 °C, 4-16 h).
- Piber, Michael,Jensen, Anne Eeg,Rottlaender, Mario,Knochel, Paul
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p. 1323 - 1326
(2008/02/09)
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- Novel Rh(I)-catalyzed reaction of arylzinc compounds with methyl halides
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The cross-coupling reactions of arylzinc compounds with methyl iodide or substituted methyl halides like benzyl bromides took place smoothly by the catalysis of Rh(I)-dppf complex.
- Hossain, Kabir M.,Takagi, Kentaro
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p. 1241 - 1242
(2007/10/03)
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- CONDENSED PYRAZOLE DERIVATIVES, METHOD OF MANUFACTURING THE SAME, AND ANDROGEN INHIBITOR
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This invention provides a condensed pyrazole derivative of the Formula (1): STR1 (where A denotes CH or N, R 0 and R 3 denote same or different, a hydrogen atom or a lower alkyl group, R 1 and R 2 denote same or different, a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkylthio group, a nitro group or a halogen atom, m denotes 1 or 2, and n denotes 1, 2 or 3, provided that, when n is 2, two R 2 may be connected to each other to form a lower alkylenedioxy group), or its pharmaceutically acceptable salt. This derivative or its salt is excellent in the effect of inhibiting the expression of action of androgen, thereby being excellent in therapeutical effect of benign prostatic hypertrophy, prostatic carcinoma, etc., and has a long lasting of efficacy and high oral absorption.
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- Pesticidal cyclopropyl-2,4-dieneamides
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The present Application discloses pesticidally active compounds of the formula (I): or a salt thereof, wherein Q is an monocyclic aromatic ring. or fused bicyclic ring system of which at least one ring is aromatic containing 9 or 10 atoms of which one may be nitrogen and the rest carbon each optionally substituted, or Q is a dihalovinyl group or a group R6 --C C-- where R6 is C1-4 alkyl, tri C1-4 alkylsilyl, halogen or hydrogen; Q1 is a 1,2-cyclopropyl ring optionally substituted by one or more groups selected from C1-3 alkyl. halo, C1-3 haloalkyl, alkynyl, or cyano; R2,R3, R4 and R5 are the same or different with at least one being hydrogen and the others being independently selected from hydrogen, halo. C1-4 alkyl or C1-4 haloalkyl; X is oxygen or sulphur; and R1 is selected from hydrogen and C1-8 hydrocarbyl optionally substituted by dioxalanyl, halo, cyano, trifluoromethyl, trifluoromethylthio or C1-6 alkoxy. their preparation, pesticidal compositions containing them and their use against pests.
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- A MILD REDUCTION OF BENZYL ALCOHOLS WITH DIPHOSPHORUS TETRAIODIDE
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On treatment with diphosphorus tetraiodide in boiling benzene, benzyl alcohols are smoothly reduced to parent hydrocarbons in good to moderate yields.
- Suzuki, Hitomi,Tani, Hiroyuki,Kubota, Hirohisa,Sato, Naofumi,Tsuji, Junko,Osuka, Atsuhiro
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p. 247 - 248
(2007/10/02)
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- SELECTIVE REDUCTION WITH LITHIUM ALUMIMIUM HYDRIDE/DIPHOSPHORUS TETRAIODIDE. A MILD CONVERSION OF AROMATIC KETONES TO PARENT HYDROCARBONS
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Treatment of aromatic ketones with the title reagent in boiling benzene gives parent hydrocarbons in good to moderate yields.
- Suzuki, Hitomi,Masuda, Reiko,Kubota, Hirohisa,Osuka, Atsuhiro
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p. 909 - 910
(2007/10/02)
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