- Diiodine-Triethylsilane System: Reduction of N-Sulfonyl Aldimines to N-Alkylsulfonamides
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Because molecular iodine and hydrosilanes are stable to both air and moisture, reactions using these reagents are easy to operate and require mild reaction conditions. Molecular iodine and a hydrosilane were used to reduce N-sulfonyl aldimines to the corr
- Jiang, Jin,Xiao, Lili,Li, Yu-Long
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supporting information
p. 291 - 294
(2020/11/09)
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- Ni(0)-Catalyzed Three-Component Coupling Reaction of Tetrafluoroethylene and N-Sulfonyl-Substituted Imines with Silanes via Aza-Nickelacycles
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A nickel-catalyzed three-component coupling reaction of tetrafluoroethylene (TFE) and N-sulfonyl-substituted imines with silanes that furnishes a variety of fluorine-containing amines is disclosed. Stoichiometric experiments revealed that the aza-nickelac
- Shirataki, Hiroshi,Ono, Takafumi,Ohashi, Masato,Ogoshi, Sensuke
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supporting information
p. 851 - 856
(2019/05/16)
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- The: N -alkylation of sulfonamides with alcohols in water catalyzed by a water-soluble metal-ligand bifunctional iridium complex [Cp?Ir(biimH2)(H2O)][OTf]2
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The iridium complex [Cp?Ir(biimH2)(H2O)][OTf]2 (Cp? = η5-pentamethylcyclopentadienyl, biimH2 = 2,2′-biimidazole) was synthesized and developed as a new-type of water-soluble metal-ligand bifunctional catalyst for the N-alkylation of poorly nucleophilic sulfonamides with alcohols in water. In the presence of catalyst (1 mol%) and Cs2CO3 (0.1 equiv.), a series of desirable products was obtained in 74-91% yields under microwave irradiation. Mechanistic experiments revealed that the presence of NH units in the imidazole ligand is crucially important for the catalytic activity of the iridium complex. Notably, this research would facilitate the process of water-soluble metal-ligand bifunctional catalysis for the hydrogen autotransfer process.
- Ai, Yao,Liu, Pengcheng,Liang, Ran,Liu, Yan,Li, Feng
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p. 10755 - 10762
(2019/07/15)
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- Nickel-Catalyzed Cross-Dehydrogenative Coupling of α-C(sp3)-H Bonds in N-Methylamides with C(sp3)-H Bonds in Cyclic Alkanes
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A nickel-catalyzed cross-dehydrogenative coupling reaction of α-C(sp3)-H bonds in N-methylamides with C(sp3)-H bonds from cyclic alkanes has been developed, which offers a cheap transition-metal-catalyzed C-H activation method for amides without the requirement for any extraneous directing group. This new strategy is highly selective and tolerates a variety of functional groups. Mechanistic investigations into the reaction process are also described in detail.
- Li, Ze-Lin,Sun, Kang-Kang,Cai, Chun
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supporting information
p. 6420 - 6424
(2018/10/15)
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- A synthetic N-alkyl sulfonamide derivatives
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The invention discloses a method for synthesizing a N-alkyl sulfonamide derivative. The method comprises the following steps: adding a sulfonamide derivative, a water-soluble catalyst, an alkali, alcohol and a solvent into a reaction container; reacting the reaction mixture at 100-120 DEG C for several hours, cooling to room temperature; performing rotary evaporation to remove the solvent, and then separating by a column to obtain the target compound. The method of the invention starts from the sulfonamide derivative, and obtains the N-alkyl sulfonamide derivative through reaction with alcohol. The method of the invention adopts a water-soluble iridium complex as a catalyst; the reaction is carried out in water; and the target compound is obtained with a high yield. Therefore, the reaction meets the requirements for green chemistry, and the method has wide development prospects.
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Paragraph 0113-0116
(2016/10/10)
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- Metal-free hydrogenation catalyzed by an air-stable borane: Use of solvent as a frustrated Lewis base
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In recent years 'frustrated Lewis pairs' (FLPs) have been shown to be effective metal-free catalysts for the hydrogenation of many unsaturated substrates. Even so, limited functional-group tolerance restricts the range of solvents in which FLP-mediated reactions can be performed, with all FLP-mediated hydrogenations reported to date carried out in non-donor hydrocarbon or chlorinated solvents. Herein we report that the bulky Lewis acids B(C6Cl5)x(C6F5)3-x (x=0-3) are capable of heterolytic H2 activation in the strong-donor solvent THF, in the absence of any additional Lewis base. This allows metal-free catalytic hydrogenations to be performed in donor solvent media under mild conditions; these systems are particularly effective for the hydrogenation of weakly basic substrates, including the first examples of metal-free catalytic hydrogenation of furan heterocycles. The air-stability of the most effective borane, B(C6Cl5)(C6F5)2, makes this a practically simple reaction method.
- Scott, Daniel J.,Fuchter, Matthew J.,Ashley, Andrew E.
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supporting information
p. 10218 - 10222
(2015/03/31)
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- The N-alkylation of sulfonamides with alcohols in water catalyzed by the water-soluble iridium complex {Cp*[6,6'-(OH)2bpy](H 2O)}[OTf]2
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The water-soluble iridium complex {Cp*[6,6'-(OH)2bpy] (H2O)}[OTf]2 (Cp=ν5-pentamethylcyclopentadienyl, bpy=2,2'-bipyridine) was found to be a general and highly efficient catalyst for the Nalkylation of the poor nucleophilic sulfonamides with alcohols as alkylating agents in water. The presence of OH units in the bpy ligand is crucially important for the catalytic activity of the iridium complex. Mechanistic investigations revealed that the catalytically active species is a ligand-metal bifunctional iridium complex bearing an N,N'-chelated 2,2'-bipyridinated ligand and an aqua ligand. Notably, the present catalytic system and the proposed mechanism provide a new horizon and scope for the development of "hydrogen autotransfer (or hydrogen-borrowing) processes".
- Qu, Panpan,Sun, Chunlou,Ma, Juan,Li, Feng
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p. 447 - 459
(2014/05/20)
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- Silylium ion promoted reduction of imines with hydrosilanes
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The silylium ion promoted reduction of imines yielding the corresponding amines is reported. Both tert-butylferrocenylmethylsilane and triethylsilane are efficient hydride donors for the reduction of intermediate silyliminium ions, thereby regenerating th
- Muether, Kristine,Mohr, Jens,Oestreich, Martin
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supporting information
p. 6643 - 6646
(2014/01/06)
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- Triflic acid catalyzed reductive coupling reactions of carbonyl compounds with O-, S-, and N-nucleophiles
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Highly efficient metal-free reductive coupling reactions of aldehydes and ketones with a range of nucleophiles in the presence of triflic acid (1-5 mol %) as the catalyst are presented. The reactions can be performed at ambient temperature without exclusion of moisture or air. A range of symmetrical and unsymmetrical ethers were obtained by this method in high yields and short reaction times. For the first time, the influence of additional functionalization has been studied. Furthermore, the formation of thioethers from ketones (by addition of unmodified thiols) and of sulfonamides from either aldehydes or ketones has been achieved under catalytic conditions.
- Gellert, Beate A.,Kahlcke, Nils,Feurer, Markus,Roth, Stefanie
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supporting information; experimental part
p. 12203 - 12209
(2011/11/07)
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- Impregnated ruthenium on magnetite as a recyclable catalyst for the N-alkylation of amines, sulfonamides, sulfinamides, and nitroarenes using alcohols as electrophiles by a hydrogen autotransfer process
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Various impregnated metallic salts on magnetite have been prepared, including cobalt, nickel, copper, ruthenium, and palladium salts, as well as a bimetallic palladium - copper derivative. Impregnated ruthenium catalyst is a versatile, inexpensive, and simple system for the selective N-monoalkylation of amino derivatives with poor nucleophilic character, such as aromatic and heteroaromatic amines, sulfonamides, sulfinamides, and nitroarenes, using in all cases alcohols as the initial source of the electrophile, through a hydrogen autotransfer process. In the case of sulfinamides, this is the first time that these amino compounds have been alkylated following this strategy, allowing the use of chiral sulfinamides and secondary alcohols to give the alkylated compound with a diastereomeric ratio of 92:8. In these cases, after alkylation, a simple acid deprotection gave the expected primary amines in good yields. The ruthenium catalyst is quite sensitive, and small modifications of the reaction medium can change the final product. The alkylation o amines using potassium hydroxide renders the N-monoalkylated amines, and the same protocol using sodium hydroxide yields the related imines. The catalyst can be easily removed by a simple magnet and can be reused up to ten times, showing the same activity.
- Cano, Rafael,Ramon, Diego J.,Yus, Miguel
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experimental part
p. 5547 - 5557
(2011/08/10)
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- N-Alkylation of poor nucleophilic amines and derivatives with alcohols by a hydrogen autotransfer process catalyzed by copper(II) acetate: Scope and mechanistic considerations
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Copper(II) acetate is a versatile, cheap and simple catalyst for the selective N-monoalkylation of amino derivatives with poor nucleophilic character, such as aromatic and heteroaromatic amines as well as carboxamides, phosphinamides, sulfonamides, and phosphazenes, using in all cases primary alcohols as initial source of the electrophiles, through a hydrogen autotransfer process. In the case of sulfonamides, the monoalkylation process followed by a naphthalene-catalyzed reductive deprotection gives primary amines, which is an indirect alternative to the direct monoalkylation of ammonia. A study of the reaction using deuterium labelled reagents was performed, indicating that the dehydrogenation and hydrogenation steps do not take placed on the same copper-atom coordination sphere, with the condensation step occurring out of the dehydrogenating catalytic species.
- Martínez-Asencio, Ana,Ramón, Diego J.,Yus, Miguel
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experimental part
p. 3140 - 3149
(2011/05/06)
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- Palladium(II) acetate as catalyst for the N-alkylation of aromatic amines, sulfonamides, and related nitrogenated compounds with alcohols by a hydrogen autotransfer process
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Palladium(II) acetate is a versatile, inexpensive, and simple catalyst for the selective N-monoalkylation of amino derivatives with poor nucleophilic character, such as aromatic and heteroaromatic amines as well as carboxamides, sulfonamides, and phosphazenes, using, in all cases, primary alcohols as the initial source of the electrophile, through a hydrogen autotransfer process. The regioselectivity of the benzothiazol-2-amine alkylation is contrary to that found using halogenated electrophiles.
- Martinez-Asencio, Ana,Yus, Miguel,Ramon, Diego J.
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experimental part
p. 3730 - 3740
(2011/12/21)
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- Simple and versatile catalytic system for N-alkylation of sulfonamides with various alcohols
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"Chemical Equation Presented" A simple and versatile catalytic system for N-alkylation of sulfonamides with various alcohols based on a catalytic hydrogen transfer reaction has been developed under a low catalyst loading of [Cp*lrCl2]2 (0.050-1.5 mol %) in the presence of t-BuOK. A variety of N-alkylated sulfonamides were prepared In good to excellent yields. Mechanistic investigations revealed that the key catalytic species in the present system is a sulfonylimido-bridged unsaturated diirldium complex [(Cp*lr)2(μ-NTs)2].
- Zhu, Mingwen,Fujita, Ken-Ichi,Yamaguchi, Ryohei
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supporting information; experimental part
p. 1336 - 1339
(2010/06/15)
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- N-Alkylation of poor nucleophilic amine and sulfonamide derivatives with alcohols by a hydrogen autotransfer process catalyzed by copper(II) acetate
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Copper(II) acetate is a versatile, cheap, and simple catalyst for the selective N-monoalkylation of amino derivatives with poor nucleophilic character, such as aromatic and heteroaromatic amines as well as sulfonamides, using in all cases primary alcohols as initial source of the electrophiles, through a hydrogen autotransfer process. In the case of sulfonamides, the monoalkylation process followed by a naphthalene-catalyzed reductive deprotection gives primary amines, which is an indirect alternative to the direct monoalkylation of ammonia.
- Martínez-Asencio, Ana,Ramón, Diego J.,Yus, Miguel
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scheme or table
p. 325 - 327
(2010/03/04)
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- Ruthenium-catalyzed /V-alkylation of amines and sulfonamides using borrowing hydrogen methodology
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The alkylation of amines by alcohols has been achieved using 0.5 mol percent [Ru(p-cymene)CI2]2 with the bidentate phosphines dppf or DPEphos as the catalyst. Primary amines have been converted into secondary amines, and secondary amines into tertiary amines, including the syntheses of Piribedil, Tripelennamine, and Chlorpheniramine. A/-Heterocyclization reactions of primary amines are reported, as well as alkylation reactions of primary sulfonamides. Secondary alcohols requiremore forcing conditions than primary alcohols but are still effective a lkylating agents in the presence of this catalyst.
- Hamid, M. Haniti S. A.,Allen, C. Liana,Lamb, Gareth W.,Maxwell, Aoife C.,Maytum, Hannah C.,et al.
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supporting information; experimental part
p. 1766 - 1774
(2009/07/25)
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- A novel procedure for the synthesis of aziridines: Application of Simmons-Smith reagents to aziridination
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The reaction of Simmons-Smith carbenoids with imines in the presence of sulfides provides N-(p-toluenesulfonyl)- and N-[(1,1,1-trimethylsilyl)ethyl]sulfonyl-substituted aziridines in high yield.
- Aggarwal, Varinder K,Stenson, Rachel A.,Jones, Ray V.H.,Fieldhouse, Robin,Blacker, John
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p. 1587 - 1589
(2007/10/03)
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- New reactivity of methoxyhydridosilane in the catalytic activation system
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Hydroxy esters are reduced by trimethoxysilane in the presence of a catalytic amount of lithium methoxide to yield diols, while for simple esters the alcohol exchange reaction takes place preferentially. Through the exchange reaction, lactones, without a hydroxy group are reduced. Tosylimines are also reduced in the system.
- Hojo, Makoto,Murakami, Chikara,Fujii, Atsuko,Hosomi, Akira
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p. 911 - 914
(2007/10/03)
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