- Secondary benzylation with benzyl alcohols catalyzed by a high-valent heterobimetallic Ir-Sn complex
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(Chemical Equation Presented) A highly efficient secondary benzylation procedure has been demonstrated using a high-valent heterobimetallic complex [Ir2(COD)2(SnCls)2(Cl)2(μ-Cl) 2] 1 as the catalyst in 1,2-dichloroethane to afford the corresponding benzylated products in moderate to excellent yields. The reaction was performed not only with carbon nucleophiles (arenes and heteroarenes) but also with oxygen (alcohol), nitrogen (amide and sulfonamide), and sulfur (thiol) nucleophiles. Mechanistic investigation showed the intermediacy of the ether in this reaction. An electrophilic mechanism is proposed from Hammett correlation.
- Podder, Susmita,Choudhury, Joyanta,Roy, Sujit
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- Direct Amination of Alcohols Catalyzed by Aluminum Triflate: An Experimental and Computational Study
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Among the best-performing homogeneous catalysts for the direct amination of activated secondary alcohols with electron-poor amine derivatives, metal triflates, such as aluminum triflate, Al(OTf)3, stand out. Herein we report the extension of this reaction to electron-rich amines and activated primary alcohols. We provide detailed insight into the structure and reactivity of the catalyst under working conditions in both nitromethane and toluene solvent, through experiment (cyclic voltammetry, conductimetry, NMR spectroscopy), and density functional theory (DFT) simulations. Competition between aniline and benzyl alcohol for Al in the two solvents explains the different reactivities. The catalyst structures predicted from the DFT calculations were validated by the experiments. Whereas a SN1-type mechanism was found to be active in nitromethane, we propose a SN2 mechanism in toluene to rationalize the much higher selectivity observed when using this solvent. Also, unlike what is commonly assumed in homogeneous catalysis, we show that different active species may be active instead of only one.
- Payard, Pierre-Adrien,Gu, Qingyi,Guo, Wenping,Wang, Qianran,Corbet, Matthieu,Michel, Carine,Sautet, Philippe,Grimaud, Laurence,Wischert, Raphael,Pera-Titus, Marc
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Read Online
- An expedient, efficient and solvent-free synthesis of T3P-mediated amidation of benzhydrols with poorly reactive N-nucleophiles under MW irradiation
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An expedient, efficient, economical, environmentally benign, and solvent free amidation protocol of benzhydrols with less reactive nitrogen nucleophiles assisted by propylphosphonic anhydride (T3P) under microwave irradiation has been developed. The methodology has been deployed for a wide range of heterocycles and electron-withdrawing & electron-donating groups. The protocol resulted in good to excellent yields under the given conditions (26 examples, 68-93% yield).
- Cheruku, Srinivas,Manikyanally, Kumara N.,Mantelingu, Kempegowda,Nagarakere, Sandhya C.,Narayana, Yatheesh,Rangappa, Kanchugarakoppal S.,Sunilkumar, Makanahalli P.
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p. 4421 - 4426
(2022/03/14)
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- Decarboxylative cross-nucleophile coupling via ligand-to-metal charge transfer photoexcitation of Cu(ii) carboxylates
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Reactions that enable carbon–nitrogen, carbon–oxygen and carbon–carbon bond formation lie at the heart of synthetic chemistry. However, substrate prefunctionalization is often needed to effect such transformations without forcing reaction conditions. The development of direct coupling methods for abundant feedstock chemicals is therefore highly desirable for the rapid construction of complex molecular scaffolds. Here we report a copper-mediated, net-oxidative decarboxylative coupling of carboxylic acids with diverse nucleophiles under visible-light irradiation. Preliminary mechanistic studies suggest that the relevant chromophore in this reaction is a Cu(ii) carboxylate species assembled in situ. We propose that visible-light excitation to a ligand-to-metal charge transfer (LMCT) state results in a radical decarboxylation process that initiates the oxidative cross-coupling. The reaction is applicable to a wide variety of coupling partners, including complex drug molecules, suggesting that this strategy for cross-nucleophile coupling would facilitate rapid compound library synthesis for the discovery of new pharmaceutical agents. [Figure not available: see fulltext.].
- Li, Qi Yukki,Gockel, Samuel N.,Lutovsky, Grace A.,DeGlopper, Kimberly S.,Baldwin, Neil J.,Bundesmann, Mark W.,Tucker, Joseph W.,Bagley, Scott W.,Yoon, Tehshik P.
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- AEROBIC OXIDATIVE SYNTHESIS OF SULFONAMIDE USING Cu CATALYST
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The present invention relates to a method for oxidative synthesis of sulfonamides using copper catalysts. , Oxygen (O) is used. 2 The oxidative synthesis of sulfonamides (1) comprises reacting a 2 th or sulfonyl hydrazide primary amine with a sulfonyl hydrazide (sulfonamide) with a copper catalyst on a solvent under the conditions in which the sulphonamide is fed. The oxidation coupling of the present invention showed extensive substrate ranges in an amine comprising a 2 primary amine, 1 primary amine and amine hydrochloride salt. It is worth notable that non-reactive aliphatic sulfonyl hydrazides in previously reported anaerobic systems can be used for the aerobic oxidation coupling of the present invention. The oxidation coupling of the present invention has been more effective on large scale.
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Paragraph 0033-0037; 0039-0054; 0139-0140
(2021/04/06)
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- Electrochemical synthesis of sulfonamides in a graphite powder macroelectrode
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The electrochemical generation of sulfinyl radicals from commercially available and non-expensive sodium salts of sulfinic acids is described. Electrooxidation reactions were carried out in a graphite powder macroelectrode using an aqueous electrolyte and cavity cell. Further reaction with primary or secondary amines gave the corresponding sulfonamides, a unit present in several biologically active compounds and pharmaceuticals, in good yields.
- Galdino, Danilo,Menezes, Paulo H.,Navarro, Marcelo,Vicente, Dmistocles A.
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supporting information
p. 5262 - 5266
(2020/09/17)
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- Nickel-Catalyzed Asymmetric Transfer Hydrogenation and α-Selective Deuteration of N-Sulfonyl Imines with Alcohols: Access to α-Deuterated Chiral Amines
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A nickel-catalyzed enantioselective transfer hydrogenation and deuteration of N-sulfonyl imines was developed. Excellent α-selectivity and high deuterium content were achieved by using inexpensive 2-propanol-d8 as a deuterium source. As a highlight, no deuteration of β-C-H and the remote C-H of N-sulfonyl amines occurred, which is hard to achieve using other imines or by hydrogen isotope exchange with D2O. Mechanism studies indicated a stepwise pathway through the [Ni-D] intermediate.
- Yang, Peng,Zhang, Li,Fu, Kaiyue,Sun, Yaxin,Wang, Xiuhua,Yue, Jieyu,Ma, Yu,Tang, Bo
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supporting information
p. 8278 - 8284
(2020/11/03)
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- Halogen-Bond-Induced Consecutive Csp3-H Aminations via Hydrogen Atom Transfer Relay Strategy
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The utilization of a halogen bond in a number of chemical fields is well-known. Surprisingly, the incorporation of this useful noncovalent interaction in chemical reaction engineering is rare. We disclose here an uncommon use of halogen bonding to induce intermolecular Csp3-H amination while enabling a hydrogen atom transfer relay strategy to access privileged pyrrolidine structures directly from alkanes. Mechanistic studies support the presence of multiple halogen bond interactions at distinct reaction stages.
- Alom, Nur-E,Ariyarathna, Jeewani P.,Bassiouni, Omar H.,Kaur, Navdeep,Kennell, Maureen L.,Li, Wei,Wu, Fan
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p. 2135 - 2140
(2020/04/09)
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- Cu-catalyzed aerobic oxidative synthesis of sulfonamides from sulfonyl hydrazides and amines
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An environmentally friendly route for sulfonamides has been developed. The oxidative coupling of sulfonyl hydrazides and amines was catalyzed by CuBr2 to produce various sulfonamides with the water and nitrogen gas as byproducts. Preliminary experiments revealed that the sulfonyl radical is likely to be involved in the reaction mechanism.
- Chung, Sohyun,Kim, Jinho
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supporting information
p. 792 - 795
(2019/02/16)
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- Pd/Zn(OTf)2 Co-Catalyzed Asymmetric Hydrogenation of Imines under Normal Pressure of Hydrogen
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An efficient method for the asymmetric hydrogenation of cyclic and acyclic N-sulfonylimines co-catalyzed by Pd/Zn(OTf)2 using hydrogen gas under ambient pressure was developed. The methodology offers an easy access to generate chiral sulfonylam
- Gao, Yang,Yang, Fan,Pu, Dongdong,Laishram, Ronibala Devi,Fan, Ruifeng,Shen, Guoli,Zhang, Xuexin,Chen, Jingchao,Fan, Baomin
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p. 6274 - 6279
(2018/11/23)
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- PTAB mediated open air synthesis of sulfonamides, thiosulfonates and symmetrical disulfanes
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A facile methodology has been described which has successfully simplified the generation of sulfonamides, thiosulfonates and symmetric disulfanes. This “trio” of reactions occur in an open air metal free atmosphere and has also been scaled up to grams making it suitable for commercialization. The reactions also have been successfully carried out with asymmetric variants, thus contributing to the chiral pool. The user friendly “trio” enables easy generation of these versatile sulfur analogues and the reaction condition employed depict an economic outline.
- Sarkar, Debayan,Ghosh, Manoj Kumar,Rout, Nilendri
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supporting information
p. 2360 - 2364
(2018/05/24)
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- Asymmetric transfer hydrogenation reactions of: N -sulfonylimines by using alcohols as hydrogen sources
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A palladium/zinc co-catalytic system was established and successfully utilized in the asymmetric transfer hydrogenation reactions of N-sulfonylimines with alcohols as hydrogen sources. Simple alcohols such as methanol, ethanol and benzyl alcohols are all
- Yang, Fan,Chen, Jingchao,Shen, Guoli,Zhang, Xuexin,Fan, Baomin
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p. 4963 - 4966
(2018/05/23)
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- Versatile and green synthesis, spectroscopic characterizations, crystal structure and DFT calculations of 1,2,3?triazole?based sulfonamides
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A green, and practically reliable method for the synthesis of novel 1,2,3?triazole-based sulfonamides via copper (I)?catalyzed azide?alkyne [3 + 2] cycloaddition reaction was reported. The desired products were characterized by CHN analysis, FT-IR, 1H and 13C NMR, ESI-MS spectroscopy, single crystal X-ray diffraction and density functional theory (DFT) geometry optimization and molecular orbital calculations. Mild and green reaction conditions, atom-economic and high yields (61–91%) make this protocol an attractive option for the synthesis of 1,2,3?triazoles bearing sulfonamide moiety. Geometrical structures, vibrational frequencies, 1H and 13C chemical shift values, Mulliken charge distribution and electrophilicity index (HOMO-LUMO analysis) of the characterized structure of 3f in the ground state have been calculated with the aid of DFT studies. The calculated chemical shifts (NMR) and vibrational frequencies (FT-IR) are in compliance with the experimental findings. The aim of the DFT study was to make a reasonable assignment of vibrational bands and chemical shifts.
- Saeidian, Hamid,Sadighian, Hamed,Abdoli, Morteza,Sahandi, Morteza
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- Efficient synthesis of novel 1,3-diyne-based sulfonamides using CuCl2/Et3N as a robust catalytic system
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An efficient and practical synthesis of 1,3-diyne-based sulfonamides using CuCl2/Et3N as a catalytic system is disclosed. Mild reaction conditions, atom-economy and high yields (50–91%) make this method an attractive option for the preparation of 1,3-diyne-based sulfonamide derivatives.
- Mirjafary, Zohreh,Sadighian, Hamed,Piri, Samira,Saeidian, Hamid
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p. 188 - 194
(2017/03/07)
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- Alkylation of Sulfonamides with Trichloroacetimidates under Thermal Conditions
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An intermolecular alkylation of sulfonamides with trichloroacetimidates is reported. This transformation does not require an exogenous acid, base, or transition metal catalyst; instead the addition occurs in refluxing toluene without additives. The sulfonamide alkylation partner appears to be only limited by sterics, with unsubstituted sulfonamides providing better yields than more encumbered N-alkyl sulfonamides. The trichloroacetimidate alkylating agent must be a stable cation precursor for the substitution reaction to proceed under these conditions.
- Wallach, Daniel R.,Chisholm, John D.
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p. 8035 - 8042
(2016/09/12)
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- Palladium-catalyzed allylic alkylation using chiral P,O-ligands synthesized via sulfonamide directed ortho-lithiation
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An efficient approach for the synthesis of chiral P,O-ligands containing sulfonamide and phosphine moieties is designed. The introduction of the chirality is achieved through different stereogenic groups attached to the sulfonamide nitrogen. The highly ef
- Petkova, Zhanina,Stoyanova, Malinka,Dimitrov, Vladimir
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p. 2093 - 2096
(2014/04/03)
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- Chemoselective hydroamination of vinyl arenes catalyzed by an NHC-amidate-alkoxide Pd(II) complex and p-TsOH
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The hydroamination of various substituted vinyl arenes with benzenesulfonamide was explored using an NHC-amidate-alkoxide palladium catalyst in conjunction with p-TsOH. Utilizing halide-substituted and electron-rich vinyl arenes, this methodology selectively furnished the cross-coupled hydroamination products in moderate to excellent yields in a Markovnikov fashion while greatly reducing undesired acid-catalyzed homocoupling of the vinyl arenes. Electron-rich vinyl arenes typically required milder conditions than electron-poor ones. While most effective for para-substituted substrates, the catalyst system also furnished the desired products from ortho- and meta-substituted vinyl arenes with high chemoselectivities.
- Giles, Richard,O'Neill, Justin,Lee, Joo Ho,Chiu, Michael K.,Jung, Kyung Woon
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p. 4083 - 4085
(2013/07/25)
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- Nonheme iron-mediated amination of C(sp3)-H bonds. Quinquepyridine-supported iron-imide/nitrene intermediates by experimental studies and DFT calculations
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The 7-coordinate complex [Fe(qpy)(MeCN)2](ClO4) 2 (1, qpy = 2,2′:6′,2″:6″, 2′′′:6′′′,2′′′′- quinquepyridine) is a highly active nonheme iron catalyst for intra- and intermolecular amination of C(sp3)-H bonds. This complex effectively catalyzes the amination of limiting amounts of not only benzylic and allylic C(sp3)-H bonds of hydrocarbons but also the C(sp3)-H bonds of cyclic alkanes and cycloalkane/linear alkane moieties in sulfamate esters, such as those derived from menthane and steroids cholane and androstane, using PhI=NR or "PhI(OAc)2 + H2NR" [R = Ts (p-toluenesulfonyl), Ns (p-nitrobenzenesulfonyl)] as nitrogen source, with the amination products isolated in up to 93% yield. Iron imide/nitrene intermediates [Fe(qpy)(NR)(X)]n+ (CX, X = NR, solvent, or anion) are proposed in these amination reactions on the basis of experimental studies including ESI-MS analysis, crossover experiments, Hammett plots, and correlation with C-H bond dissociation energies and with support by DFT calculations. Species consistent with the formulations of [Fe(qpy)(NTs)2] 2+ (CNTs) and [Fe(qpy)(NTs)]2+ (C) were detected by high-resolution ESI-MS analysis of the reaction mixture of 1 with PhI=NTs (4 equiv). DFT calculations revealed that the reaction barriers for H-atom abstraction of cyclohexane by the ground state of 7-coordinate C NTs and ground state of C are 15.3 and 14.2 kcal/mol, respectively, in line with the observed high activity of 1 in catalyzing the C-H amination of alkanes under mild conditions.
- Liu, Yungen,Guan, Xiangguo,Wong, Ella Lai-Ming,Liu, Peng,Huang, Jie-Sheng,Che, Chi-Ming
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supporting information
p. 7194 - 7204
(2013/06/27)
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- FeCl3-catalyzed addition of nitrogen and 1,3-dicarbonyl nucleophiles to olefins
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A direct intermolecular addition of nitrogen and 1,3-dicarbonyl nucleophiles to stabilized double bonds (styrenes, 1,3-dienes, enol-ethers, sugars.) in the presence of green and inexpensive FeCl3 catalyst is described.
- Zotto, Christophe Dal,Michaux, Julien,Zarate-Ruiz, Araceli,Gayon, Eric,Virieux, David,Campagne, Jean-Marc,Terrasson, Vincent,Pieters, Grégory,Gaucher, Anne,Prim, Damien
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experimental part
p. 296 - 304
(2011/02/17)
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- Amberlyst-15 in ionic liquid: An efficient and recyclable reagent for nucleophilic substitution of alcohols and hydroamination of alkenes
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The nucleophilic substitution reaction of secondary alcohols and hydroamination of alkenes with amides, sulfonamides, carbamates, and amines using Amberlyst-15 immobilized in [Bmim][BF4] (1-butyl-3- methylimidazolium tetrafluoroborate) ionic liquid as an efficient recyclable reagent is described. The solvent effect is prominent in the reaction, and the desired substitution products are obtained in good to excellent yield. The protocol is advantageous due to the ease of handling of the reagents, the simple work-up procedure, and the environmentally benign conditions that allow effective recyclability. A facile protocol involving Amberlyst-15 in the ionic liquid [Bmim][BF4] (= 1-butyl-3-methylimidazolium tetrafluoroborate) has been developed for nucleophilic substitution of alcohols and hydroamination of alkenes.
- Qureshi, Ziyauddin S.,Deshmukh, Krishna M.,Tambade, Pawan J.,Dhake, Kishor P.,Bhanage, Bhalchandra M.
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experimental part
p. 6233 - 6238
(2010/12/25)
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- Ni(0)-catalyzed formation of azaaluminacyclopentenes via azanickelacyclopentenes: A unique nickel/aluminum double transmetalation reaction
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(Chemical Equation Presented) Azaaluminacyclopentenes, which serve as useful precursors for γ-substituted allylamines, were catalytically prepared from novel Ni-mediated three-component cyclocondensation of an alkyne, an imine, and AlMe3.
- Ohashi, Masato,Kishizaki, Osamu,Ikeda, Haruo,Ogoshi, Sensuke
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supporting information; experimental part
p. 9160 - 9161
(2009/12/06)
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- Iodine-catalyzed intermolecular hydroamination of vinyl arenes
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The vinyl arenes undergo smooth hydroamination with sulfonamides in the presence of 10 mol % of iodine to furnish tosyl and mesyl-protected secondary amines in excellent yields in short reaction times. The use of inexpensive and readily available molecula
- Yadav,Reddy, B.V. Subba,Rao, T. Srinivasa,Krishna, B. Bala M.
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experimental part
p. 5351 - 5353
(2009/12/06)
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- Copper triflate/t-BuOOAc-catalyzed amidation of allylic and benzylic acetates with sulfonamides
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A copper triflate/t-BuOOAc-catalyzed amidation of allylic and benzylic acetates has been developed which is suitable for the coupling of a wide variety of functionalized sulfonamide nucleophiles with acetate electrophiles. The methodology allows for the amidation of benzylic substrates which are not further activated by an additional adjacent alkene or alkyne, enabling simple allylic acetates and primary benzylic acetates to be used as reaction partners.
- Powell, David A.,Pelletier, Guillaume
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p. 2495 - 2498
(2008/09/19)
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- Efficient intermolecular iron-catalyzed amidation of C-H bonds in the presence of n-bromosuccinimide
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We have developed an efficient, inexpensive, and air-stable catalyst/oxidant (FeCI2/NBS) system that could efficiently promote amidation of benzylic sp3 C-H bonds in ethyl acetate under mild conditions.
- Wang, Zhe,Zhang, Yongming,Fu, Hua,Jiang, Yuyang,Zhao, Yufen
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supporting information; experimental part
p. 1863 - 1866
(2009/04/12)
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- Nickel-catalysed addition of dialkylzinc reagents to N-phosphinoyl- and N-sulfonylimines
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A catalytic amount of a nickel complex (0.1-5.3 mol %) extraordinarily increases the reaction rate of the addition of dialkylzinc reagents to N-(diphenylphosphinoyl)- or N-(benzenesulfonyl)imines. The reaction of imines derived from both aromatic and alip
- Almansa, Raquel,Guijarro, David,Yus, Miguel
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p. 1167 - 1174
(2007/10/03)
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- Intermodular FeCl3-catalyzed hydroamination of styrenes
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Hydroamination reactions of vinylarenes with nonnucleophilic nitrogen derivatives (p-toluenesulfonamide, p-nitroaniline, p-nitrobenzamide, ...) catalyzed by FeCl3 are described. Interestingly, these reactions are catalyzed by an environmentally
- Michaux, Julien,Terrasson, Vincent,Marque, Sylvain,Wehbe, Johny,Prim, Damien,Campagne, Jean-Marc
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p. 2601 - 2603
(2008/02/06)
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- Copper-catalyzed amidation of allylic and benzylic C-H bonds
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(Chemical Equation Presented) A copper-catalyzed amidation of allylic and benzylic C-H bonds with both primary and secondary sulfonamides is described. The reaction is applicable to the coupling of a diverse set of hydrocarbon species with aryl, heteroaryl, and alkyl sulfonamides and is tolerant of a variety of functional groups. Mechanistic insight has been gained through the isolation of a benzylic acetate intermediate, which was demonstrated to undergo facile conversion to the substituted sulfonamide product under copper catalysis.
- Pelletier, Guillaume,Powell, David A.
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p. 6031 - 6034
(2007/10/03)
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- Imido transfer from bis(imido)ruthenium(VI) porphyrins to hydrocarbons: Effect of imido substituents, C-H bond dissociation energies, and Ru VI/V reduction potentials
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[RuVI(TMP)(NSO2R)2] (SO2R = Ms, Ts, Bs, Cs, Ns; R = p-C6H4OMe, p-C6H 4Me, C6H5, p-C6H4-Cl, p-C6H4NO2, respectively) and [Ru VI(Por)(NTs)2] (Por = 2,6-Cl2TPP, F 20-TPP) were prepared by the reactions of [RuII(Por)(CO)] with Phl=NSO2R in CH2Cl2. These complexes exhibit reversible RuVI/V couple with E1/2 = -0.41 to -0.12 V vs Cp2Fe+/10 and undergo imido transfer reactions with styrenes, norbornene, cis-cyclooctene, indene, ethylbenzenes, cumene, 9,10-dihydroanthracene, xanthene, cyclohexene, toluene, and tetrahydrofuran to afford aziridines or amides in up to 85% yields. The second-order rate constants (k2) of the aziridination/amidation reactions at 298 K were determined to be (2.6 ± 0.1) × 10-5 to 14.4 ± 0.6 dm3 mol-1 s-1, which generally increase with increasing RuVI/V reduction potential of the imido complexes and decreasing C-H bond dissociation energy (BDE) of the hydrocarbons. A linear correlation was observed between log K (K is the k2 value divided by the number of reactive hydrogens) and BDE and between log k2 and E1/2(RuVI/V); the linearity in the former case supports a H-atom abstraction mechanism. The amidation by [RuVI(TMP)(NNs) 2] reverses the thermodynamic reactivity order cumene > ethylbenzene/toluene, with K(3° C-H)/K(2° C-H) = 0.2 and K(3° C-H)/K(1° C-H) = 0.8.
- Leung, Sarana Ka-Yan,Tsui, Wai-Man,Huang, Jie-Sheng,Che, Chi-Ming,Liang, Jiang-Lin,Zhu, Nianyong
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p. 16629 - 16640
(2007/10/03)
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- Reaction of indium ate complexes with allylic compounds. Controlling S N2/SN2′ selectivity by solvents
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Vinyl and methylindium ate complexes (indates) were prepared and both the tendency of immigration and regioselectivity toward cinnamyl bromide were investigated. The vinyl group was more preferably transferred than the Me group, giving a regioisomeric mixture of SN2 and SN2′ products. The ratio of SN2/SN2′ selectivity can be controlled by solvents; in the presence of polar solvents, such as N-butylpyrrolidone (NBP) and THF, the SN2′ product was mainly obtained, whereas the SN2 product was selectively prepared in solutions containing hexane. The vinylindium compound, generated by the reaction of allylic-type diindium reagents with imine, was also converted to the corresponding vinyl indate, which was allowed to react with allyl chloride to give a three-component coupling product.
- Hirashita, Tsunehisa,Hayashi, Yousuke,Mitsui, Kazuma,Araki, Shuki
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p. 3225 - 3228
(2007/10/03)
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