- Small Phosphine Ligands Enable Selective Oxidative Addition of Ar-O over Ar-Cl Bonds at Nickel(0)
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Current methods for Suzuki-Miyaura couplings of nontriflate phenol derivatives are limited by their intolerance of halides including aryl chlorides. This is because Ni(0) and Pd(0) often undergo oxidative addition of organohalides at a similar or faster rate than most Ar-O bonds. DFT and stoichiometric oxidative addition studies demonstrate that small phosphines, in particular PMe3, are unique in promoting preferential reaction of Ni(0) with aryl tosylates and other C-O bonds in the presence of aryl chlorides. This selectivity was exploited in the first Ni-catalyzed C-O-selective Suzuki-Miyaura coupling of chlorinated phenol derivatives where the oxygen-containing leaving group is not a fluorinated sulfonate such as triflate. Computational studies suggest that the origin of divergent selectivity between PMe3 and other phosphines differs from prior examples of ligand-controlled chemodivergent cross-couplings. PMe3 effects selective reaction at tosylate due to both electronic and steric factors. A close interaction between nickel and a sulfonyl oxygen of tosylate during oxidative addition is critical to the observed selectivity.
- Entz, Emily D.,Hooker, Leidy V.,Neufeldt, Sharon R.,Russell, John E. A.
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supporting information
p. 15454 - 15463
(2020/10/18)
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- The Synthesis and Catalytic Activity of New Mixed NHC-Phosphite Nickel(0) Complexes
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Herein we describe the synthesis and isolation of the first low-valent NHC-phosphite nickel complexes of general formula Ni(NHC)[P(OAr)3]2. These three-coordinate Ni(0) compounds were fully characterized, including by X-ray crystallography that highlighted their trigonal planar geometry. The representative complex Ni(IMes)[P(OPh)3]2 was used to show that a phosphite ligand is readily substituted in the presence of an aldehyde or nitrile. These stoichiometric studies then led to an investigation of their catalytic properties in the Suzuki-Miyaura cross-coupling reactions between aryl tosylates and aryl boronic acids, a first for such a NHC-Ni catalyst. Finally, mechanistic investigations led to the isolation of a well-defined oxidative addition product.
- Dorta, Reto,Duczynski, Jeremy,Moggach, Stephen A.,Sobolev, Alexandre N.,Stewart, Scott G.
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supporting information
(2020/01/21)
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- Copper-Catalyzed C-S Bond Formation via the Cleavage of C-O Bonds in the Presence of S8 as the Sulfur Source
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Useful and applicable methods for one-pot and odorless synthesis of unsymmetrical and symmetrical diaryl sulfides via C-O bond activation are presented. First, a new efficient procedure for the synthesis of unsymmetrical sulfides using the cross-coupling reaction of phenolic esters such as acetates, tosylates, and triflates and with arylboronic acid or triphenyltin chloride as the coupling partners is reported. Depending on the reaction, S 8 /KF or S 8 /NaO t -Bu system is found to be an effective source of sulfur in the presence of copper salts and in poly(ethylene glycol) as a green solvent. Then, the synthesis of symmetrical diaryl sulfides from phenolic compounds by using S 8 as the sulfur source and NaO t -Bu in anhydrous DMF at 120 °C under N 2 is described. By these protocols, the synthesis of a variety of unsymmetrical and symmetrical sulfides become easier than the available protocols in which thiols and aryl halides are directly used for the preparation of the sulfides.
- Rostami, Abed,Rostami, Amin,Ghaderi, Arash,Gholinejad, Mohammad,Gheisarzadeh, Sajedeh
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p. 5025 - 5038
(2017/10/06)
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- Chromatography-Free and Eco-Friendly Synthesis of Aryl Tosylates and Mesylates
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Two chromatography-free and eco-friendly protocols have been developed to synthesize aryl tosylates and mesylates by the tosylation and mesylation of the corresponding hydroxyarenes, respectively. These protocols are superior to other known ones regarding
- Lei, Xiangyang,Jalla, Anusha,Abou Shama, Mhd A.,Stafford, Jamie M.,Cao, Billy
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supporting information
p. 2578 - 2585
(2015/09/01)
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- Iodine-induced synthesis of sulfonate esters from sodium sulfinates and phenols under mild conditions
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An iodine-induced synthesis of sulfonate esters via cross-coupling reactions of sodium sulfinates with phenols is reported. This synthetic route is low-cost, facile, green and efficient, and could afford the target products with good to excellent yields u
- Gao, Jian,Pan, Xiaojun,Liu, Juan,Lai, Junyi,Chang, Liming,Yuan, Gaoqing
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p. 27439 - 27442
(2015/03/31)
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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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- Copper-catalysed coupling of aryl tosylates with sodium arylsulfinates
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Diaryl sulfones derivatives were easily synthesised from aryl tosylates and sodium arylsulfinates in high yields using [Cu(CH3CN)4]PF6 as catalyst. The transformation is efficient, simple and the starting materials are readily available.
- Wang, Chunjie,Zhang, Hui,Li, Zhiwei,Wang, Ziyun
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p. 639 - 642
(2015/02/02)
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- Nickel-catalyzed C-P coupling of aryl mesylates and tosylates with H(O)PR1R2
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A method was developed for the nickel-catalyzed phosphonylation of aryl mesylates and tosylates with H(O)PR1R2. To the best of our knowledge, this is the first example of nickel-catalyzed C-P coupling of aryl mesylates and tosylates. Most of the substrates gave moderate to good yields under our catalytic system.
- Shen, Chaoren,Yang, Guoqiang,Zhang, Wanbin
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supporting information; body text
p. 3500 - 3505
(2012/05/20)
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- 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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supporting information; experimental part
p. 1800 - 1801
(2010/04/24)
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- Highly efficient Pd-catalyzed cyanation of aryl chlorides and arenesulfonates with potassium ferrocyanide in aqueous media
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A highly improved Pd-catalyzed cyanation of aryl chlorides to corresponding benzonitriles was demonstrated in aqueous media. Moreover, Pd-catalyzed cyanation of aryl tosylates and benzenesulfonates with K4[Fe(CN) 6] was developed under the similar conditions, which extended application scope of the cyanation. Graphical Abstract: [Figure not available: see fulltext.]
- Zhang, Junli,Chen, Xiaorong,Hu, Tongjie,Zhang, Yuan,Xu, Kunling,Yu, Yanpeng,Huang, Jun
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experimental part
p. 56 - 60
(2011/01/12)
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- Palladium-catalyzed amination of aryl and heteroaryl tosylates at room temperature
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Mild palladium-catalyzed aminations of aryl tosylates and the first aminations of heteroaryl tosylates are described. In the presence of the combination of L2Pd(0) (L = P(o-tol)3) and the hindered Josiphos ligand CyPF-t-Bu, a variety of primary alkylamines and arylamines react with both aryl and heteroaryl tosylates at room temperature to form the corresponding secondary arylamines in high yields with complete selectivity for the monoarylamine. These reactions at room temperature occur in many cases with catalyst loadings of 0.1 mol % and 0.01 mol % in one case, constituting the most efficient aminations of aryl tosylates by nearly 2 orders of magnitude. This catalyst is made practical by the development of a convenient method to synthesize the L2Pd(0) precursor. This complex is stable to air as a solid. In contrast to conventional relative rates for reactions of aryl sulfonates, the reactions of aryl tosylates are faster than parallel reactions of aryl triflates, and the reactions of aryl tosylates are faster than parallel or competitive reactions of aryl chlorides. Copyright
- Ogata, Tokutaro,Hartwig, John F.
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supporting information; experimental part
p. 13848 - 13849
(2009/02/07)
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- New preparative method of aryl tosylates by using organobismuth reagents
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A new method for the preparation of aryl tosylates by using pentavalent bismuth is described. Treatment of 10-arylphenothiabismine 5,5-dioxides, m-chloroperoxybenzoic acid (MCPBA) and p-toluenesulfonic acid monohydrate in dichloromethane affords aryl tosy
- Sakurai, Naoto,Mukaiyama, Teruaki
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p. 928 - 929
(2008/02/12)
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- A new preparative method of aryl sulfonate esters by using cyclic organobismuth reagents
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A new method for the preparation of aryl sulfonate esters by using a cyclic pentavalent bismuth is described. Aryl sulfonate esters are formed in good to high yields by treating 10-arylphenothiabismine 5,5-dioxides, m-chloroperoxybenzoicacid (m-CPBA)and various sulfonic acids in dichloromethane.
- Sakurai, Naoto,Mukaiyama, Teruaki
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p. 771 - 790
(2008/09/18)
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- Solvent-free and selective tosylation of alcohols and phenols with p-toluenesulfonyl chloride by heteropolyacids as highly efficient catalysts
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Tosylation of some alcohols and phenols has been directly carried out with p-toluenesulfonyl chloride using heterodoxy acids (H3PW 12O40, H3PMo12O40, A 3PW12O40, and AlPMo12O40) as catalysts in the absence of solvent. We found that heteropoly acids AlPW12O40 and AlPMo 12O40 were effective catalysts for the tosylation of alcohols and phenols. In the case of aliphatic alcohols, secondary alcohols undergo tosylation chemoselectively in the presence of primary hydroxyl groups. This new method consistently has the advantage of excellent yields and short reaction time.
- Fazaeli, Razieh,Tangestaninejad, Shahram,Aliyan, Hamid
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p. 812 - 818
(2007/10/03)
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- Graphite/methanesulfonic acid (GMA) as a new reagent for sulfonylation of phenols and thia-Fries rearrangement of aryl sulfonates to sulfonylphenols
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A new facile method for direct sulfonylation of phenols was developed. Graphite in methanesulfonic acid (GMA) was used to prepare sulfonylphenols by sulfonylation of phenol and naphthalene derivatives with p-toluenesulfonic acid (=4-methylbenzenesulfonic acid) (Table 1) and the thia-Fries rearrangement of aryl sulfonates (Table 4). Mechanistic studies showed that the sulfonylation reaction of phenols in GMA occurred through an initial sulfonate formation followed by a thia-Fries rearrangement of the aryl sulfonate by an intermolecular mechanism (Scheme 3).
- Sharghi, Hashem,Shahsavari-Fard, Zahra
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- Solvent-Free Synthesis of Aryl Tosylates under Microwave Activation
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Synthesis of aryl tosylates from phenols requires only several minutes when conducted with controlled microwave heating under solvent-free condition. Eight different aryl tosylates were synthesized and isolated in good yields.
- Xu, Li-Wen,Xia, Chun-Gu
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p. 1199 - 1205
(2007/10/03)
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- Room-Temperature Ni(0)-Catalyzed Cross-Coupling Reactions of Aryl Arenesulfonates with Arylboronic Acids
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Room-temperature Ni(0)-catalyzed cross-coupling reactions of aryl arenesulfonates with arylboronic acids are described. The Ni(0) catalyst, derived from Ni(COD)2 and PCy3, proved to be a general one for the Suzuki?Miyaura cross-coupling of a variety of aryl arenesulfonates. The mild reaction condition, the readily availability of the catalyst, and excellent coupling yields make aryl arenesulfonates potentially useful substrates in organic synthesis. Copyright
- Tang, Zhen-Yu,Hu, Qiao-Sheng
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p. 3058 - 3059
(2007/10/03)
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- NiCl2(PCy3)2: A simple and efficient catalyst precursor for the Suzuki cross-coupling of aryl tosylates and arylboronic acids
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matrix presented NiCl2(PCy3)2 associated with PCy3 promotes the selective cross-coupling of aryltosylates with arylboronic acids under relatively mild reaction conditions, and a variety of functional groups are tolerated in both arenes. This is one of the simplest and most efficient experimental procedures for the coupling of arylboronic acids with aryl tosylates reported to date.
- Zim, Danilo,Lando, Vanusa R.,Dupont, Jairton,Monteiro, Adriano L.
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p. 3049 - 3051
(2007/10/03)
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