- Synthesis of Polysubstituted Fused Pyrroles by Gold-Catalyzed Cycloisomerization/1,2-Sulfonyl Migration of Yndiamides
-
Yndiamides (bis-N-substituted alkynes) are valuable precursors to azacycles. Here we report a cycloisomerization/1,2-sulfonyl migration of alkynyl-yndiamides to form tetrahydropyrrolopyrroles, unprecedented heterocyclic scaffolds that are relevant to medicinal chemistry. This functional group tolerant transformation can be achieved using Au(I) catalysis that proceeds at ambient temperature, and a thermally promoted process. The utility of the products is demonstrated by a range of reactions to functionalize the fused pyrrole core.
- Smith, Philip J.,Jiang, Yubo,Tong, Zixuan,Pickford, Helena D.,Christensen, Kirsten E.,Nugent, Jeremy,Anderson, Edward A.
-
supporting information
p. 6547 - 6552
(2021/08/30)
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- Electrochemical synthesis of sulfonamides in a graphite powder macroelectrode
-
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)
-
- Boron-Catalyzed N-Alkylation of Arylamines and Arylamides with Benzylic Alcohols
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A sustainable boron-based catalytic approach for chemoselective N-alkylation of primary and secondary aromatic amines and amides with primary, secondary, and tertiary benzylic alcohols has been presented. The metal-free protocol operates at low catalyst loading, tolerates several functional groups, and generates H2O as the sole byproduct. Preliminary mechanistic studies were performed to demonstrate the crucial role of boron catalyst for the activation of the intermediate dibenzyl ether and to identify the rate-determining step.
- Guru, Murali Mohan,Thorve, Pradip Ramdas,Maji, Biplab
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p. 806 - 819
(2020/01/02)
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- Method for synthesizing N-alkyl sulfonamide in water
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The invention discloses a method for synthesizing N-alkyl sulfonamide in water, in particular to a method for synthesizing an N-alkyl sulfonamide derivative from a sulfonamide derivative and alcohol,and a water-soluble iridium complex is adopted to catalyze the reaction of N-alkyl sulfonamide. Compared with the previous synthesis method, the method has the advantages that a reaction equivalent substrate is used in the reaction process, so that raw material waste is avoided; weak base is used, and reaction conditions are mild; non-toxic and harmless pure water is used as a solvent in the reaction, only water is generated as a by-product, the atom reaction economy is high, and the requirement of green chemistry is met.
- -
-
Paragraph 0043; 0044; 0045; 0046; 0047
(2020/12/30)
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- Methyl-triflate-mediated dearylmethylation of: N -(arylmethyl)carboxamides via the retro-Mannich reaction induced by electrophilic dearomatization/rearomatization in an aqueous medium at room temperature
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We have developed a protocol for the dearylmethylation of N-(arylmethyl)carboxamides under metal-free conditions in an aqueous medium at room temperature. This protocol involves methyl triflate-mediated successive C-C and C-N bond cleavages (retro-Mannich reaction) induced by electrophilic dearomatization/rearomatization. The dearomatization/rearomatization strategy can be expected to inspire the development of novel transformations based on the C-C bond cleavage in an environmentally benign manner.
- Peng, Hui,Ma, Jinhui,Luo, Wenkun,Zhang, Guangwen,Yin, Biaolin
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p. 2252 - 2256
(2019/05/17)
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- Manganese-Catalyzed N-Alkylation of Sulfonamides Using Alcohols
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An efficient manganese-catalyzed N-alkylation of sulfonamides has been developed. This borrowing hydrogen approach employs a well-defined and bench-stable Mn(I) PNP pincer precatalyst, allowing benzylic and simple primary aliphatic alcohols to be employed as alkylating agents. A diverse range of aryl and alkyl sulfonamides undergoes mono-N-alkylation in excellent isolated yields (32 examples, 85% average yield).
- Reed-Berendt, Benjamin G.,Morrill, Louis C.
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p. 3715 - 3724
(2019/03/30)
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- A bifunctional strategy for N-heterocyclic carbene-stabilized iridium complex-catalyzed: N -alkylation of amines with alcohols in aqueous media
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Through the strategy of combining bifunctional 2-hydroxypyridine and a thermally stable N-heterocyclic carbene ligand, an Ir-catalyzed N-monoalkylation reaction has been developed in aqueous media under base-free conditions. This reaction proceeds smoothly with high yields of various aromatic amines and sulfonamides with a wide range of primary alcohols. Experimental and computational studies revealed a metal-ligand cooperative mechanism and its thermal stability during the bifunctional catalysis in aqueous media.
- Huang, Ming,Li, Yinwu,Liu, Jiahao,Lan, Xiao-Bing,Liu, Yan,Zhao, Cunyuan,Ke, Zhuofeng
-
supporting information
p. 219 - 224
(2019/01/28)
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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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- Synthesis, Characterization, and Reactivity of an Ethynyl Benziodoxolone (EBX)-Acetonitrile Complex
-
The synthesis of a crystalline ethynyl-1,2-benziodoxol-3(1H)-one (EBX)-acetonitrile complex is described. EBX has been widely used as an active species for a variety of reactions; however, its high instability has so far prevented its isolation. The EBX-acetonitrile is self-assembled into a double-layered honeycomb structure through weak hypervalent iodine secondary interactions and hydrogen bonding. The N-ethynylation of a variety of sulfonamides using the EBX-acetonitrile complex as a substrate under mild conditions is also described.
- Yudasaka, Masaharu,Shimbo, Daisuke,Maruyama, Toshifumi,Tada, Norihiro,Itoh, Akichika
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supporting information
p. 1098 - 1102
(2019/05/16)
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- A Micellar Catalysis Strategy for Amidation of Alkynyl Bromides: Synthesis of Ynamides in Water
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Copper-catalyzed amidation of alkynyl bromides can be carried out in water for the first time, which is made possible by a micellar catalysis strategy using rosin-based surfactant APGS-550-M. The surfactant can be easily prepared from natural abundant biomass, resin acids. Studies as to substrate scope and reaction aqueous medium recycling showcase the ease and sustainability of this technology.
- Yang, Yunqin,Meng, Xiangtai,Zhu, Baolong,Jia, Ying,Cao, Xiaoji,Huang, Shenlin
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supporting information
p. 1166 - 1169
(2019/01/04)
-
- Visible-light, iodine-promoted formation of n-sulfonyl imines and n-alkylsulfonamides from aldehydes and hypervalent iodine reagents
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Alternative synthetic methodology for the direct installation of sulfonamide functionality is a highly desirable goal within the domain of drug discovery and development. The formation of synthetically valuable N-sulfonyl imines from a range of aldehydes,
- Hopkins, Megan D,Brandeburg, Zachary C.,Hanson, Andrew J.,Lamar, Angus A
-
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- Catalytic Dearomative Spirocyclization via Gold Carbene Species Derived from Ynamides: Efficient Synthesis of 2-Azaspiro[4.5]decan-3-ones
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An intramolecular catalytic dearomatization of phenols via gold carbene species proceeded to provide 2-azaspiro[4.5]decan-3-ones. The use of NHC ligand and water as a co-solvent was critical for achieving high reactivity. This reaction did not require hazardous diazo compounds as carbene sources and proceeded even under air. The obtained spirocyclic product could be readily transformed into a gabapentin derivative by hydrogenation and deprotection.
- Ito, Mamoru,Kawasaki, Ryosuke,Kanyiva, Kyalo Stephen,Shibata, Takanori
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supporting information
p. 3721 - 3724
(2018/02/23)
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- Enantioselective Synthesis of trans-Vicinal Diamines via Rhodium-Catalyzed [2+2] Cycloaddition of Allenamides
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An efficient protocol for the enantioselective Rh-catalyzed intermolecular head-to-head [2+2] cycloaddition of allenamides was developed. A variety of enantio-enriched cyclobutane-1,2-diamine derivatives were achieved in good yields with good to excellent enantioselectivities. (Figure presented.).
- Zheng, Wei-Feng,Sun, Gui-Jun,Chen, Liang,Kang, Qiang
-
supporting information
p. 1790 - 1794
(2018/04/02)
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- Enantioselective, intermolecular benzylic C-H amination catalysed by an engineered iron-haem enzyme
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C-H bonds are ubiquitous structural units of organic molecules. Although these bonds are generally considered to be chemically inert, the recent emergence of methods for C-H functionalization promises to transform the way synthetic chemistry is performed. The intermolecular amination of C-H bonds represents a particularly desirable and challenging transformation for which no efficient, highly selective, and renewable catalysts exist. Here we report the directed evolution of an iron-containing enzymatic catalyst - based on a cytochrome P450 monooxygenase - for the highly enantioselective intermolecular amination of benzylic C-H bonds. The biocatalyst is capable of up to 1,300 turnovers, exhibits excellent enantioselectivities, and provides access to valuable benzylic amines. Iron complexes are generally poor catalysts for C-H amination: in this catalyst, the enzyme's protein framework confers activity on an otherwise unreactive iron-haem cofactor.
- Prier, Christopher K.,Zhang, Ruijie K.,Buller, Andrew R.,Brinkmann-Chen, Sabine,Arnold, Frances H.
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p. 629 - 634
(2017/06/30)
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- Nondirected, cu-catalyzed sp3 C-H aminations with hydroxylamine-based amination reagents: Catalytic and mechanistic studies
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This work demonstrates the use of hydroxylamine-based amination reagents RSO2NH-OAc for the nondirected, Cu-catalyzed amination of benzylic C-H bonds. The amination reagents can be prepared on a gram scale, are benchtop stable, and provide benzylic C-H amination products with up to 86% yield. Mechanistic studies of the established reactivity with toluene as substrate reveal a ligand-promoted, Cu-catalyzed mechanism proceeding through Ph-CH2(NTsOAc) as a major intermediate. Stoichiometric reactivity of Ph-CH2(NTsOAc) to produce Ph-CH2-NHTs suggests a two-cycle, radical pathway for C-H amination, in which the decomposition of the employed diimine ligands plays an important role.
- Wang, Anqi,Venditto, Nicholas J.,Darcy, Julia W.,Emmert, Marion H.
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p. 1259 - 1268
(2017/05/29)
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- Metal-Free Benzylic C?H Amination via Electrochemically Generated Benzylaminosulfonium Ions
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Electrochemical oxidation of toluene derivatives in the presence of N-tosyldiphenylsulfilimine gave the corresponding benzylaminosulfonium ions, which were treated with tetrabutylammonium iodide under non-electrolytic conditions to give N-tosylbenzylamines. The transformation serves as a metal- and chemical-oxidant-free method for benzylic C?H amination. Because of high oxidation potential of N-tosyldiphenylsulfilimine the present method can be applied to synthesis of various benzylamines from functionalized toluene derivatives.
- Hayashi, Ryutaro,Shimizu, Akihiro,Song, Yetao,Ashikari, Yosuke,Nokami, Toshiki,Yoshida, Jun-Ichi
-
supporting information
p. 61 - 64
(2017/01/09)
-
- Hydrogen autotransfer and related dehydrogenative coupling reactions using a rhenium(i) pincer catalyst
-
A novel rhenium complex bearing a non-innocent PNP pincer ligand was prepared. This novel catalyst is active in hydrogen autotransfer reactions to form new C-C and C-N bonds. More specifically, valuable alkylations of ketones and sulfonamides with primary alcohols are herein presented. In addition, the first examples of rhenium-catalysed synthesis of pyrroles are described by dehydrogenative coupling of diols, amines and ketones.
- Piehl, Patrick,Pe?a-López, Miguel,Frey, Anna,Neumann, Helfried,Beller, Matthias
-
supporting information
p. 3265 - 3268
(2017/03/20)
-
- An eco-friendly tandem tosylation/Ferrier N-glycosylation of amines catalyzed by Er(OTf)3 in 2-MeTHF
-
Er(OTf)3 in 2-MeTHF provides a new and eco-friendly process for Ferrier glycosylation of sulfonamides and amino acids with various N-nucleophiles. The stereoselective synthesis of 2,3-unsaturated-N-pseudoglycals was carried out with 3,4,6-tri-O-acetyl-D-glucal and different nucleophiles affording good results in a short time.
- Nardi, Monica,Cano, Natividad Herrera,De Nino, Antonio,Di Gioia, Maria Luisa,Maiuolo, Loredana,Oliverio, Manuela,Santiago, Ana,Sorrentino, Diletta,Procopio, Antonio
-
supporting information
p. 1721 - 1726
(2017/04/13)
-
- A synthetic N-alkyl sulfonamide derivatives
-
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.
- -
-
Paragraph 0043-0046
(2016/10/10)
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- Synthesis of Highly Functionalized 4-Aminoquinolines
-
A diverse set of highly substituted 4-aminoquinolines was synthesized from ynamides, triflic anhydride, 2-chloropyridine, and readily accessible amides in a mild one-step procedure. Diverse products: Electrophilically activated amides easily react with sulfonyl ynamides to yield a diverse range of substituted 4-aminoquinolines. The ynamides can be easily modified by Sonogashira processes or generated from dichloroenamide precursors. Any substituent can thus be introduced at the C3 position of the quinoline. 2-ClPy=2-chloropyridine, Tf2O=triflic anhydride.
- Wezeman, Tim,Zhong, Sabilla,Nieger, Martin,Br?se, Stefan
-
supporting information
p. 3823 - 3827
(2016/04/05)
-
- Direct Alkylation of Amines with Alcohols Catalyzed by Base
-
A base-catalyzed/promoted transition-metal-free direct alkylation of amines with alcohols has been developed, giving the desired amines in generally high yields from either aromatic or aliphatic alcohols. On the basis of the 1H NMR and in situ IR (React-IR) monitoring experiments, isotope-labeling experiments, as well as control experiments, a novel "hemiaminal" model is proposed to understand the mechanism, which explains the formation of the "extra" aldehyde in the reaction.
- Li, Qiang-Qiang,Xiao, Zu-Feng,Yao, Chuan-Zhi,Zheng, Hong-Xing,Kang, Yan-Biao
-
supporting information
p. 5328 - 5331
(2015/11/18)
-
- Aqueous MW eco-friendly protocol for amino group protection
-
In this paper a new catalyst-free and on-water method for protection of amines and amino acids with di-tert-butyl dicarbonate, 9-fluorenylmethoxycarbonyl chloride, acetyl chloride and tosyl chloride is presented. The protection can be realized in a few minutes under microwave-assistance. The reaction proved to be chemoselective in presence of ambident nucleophiles and water solution of di-tert-butyl carboxylic acid or chloride acid are the only wastes produced.
- Nardi,Cano, N. Herrera,Costanzo,Oliverio,Sindona,Procopio
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p. 18751 - 18760
(2015/06/15)
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- CuI-catalyzed coupling of gem-dibromovinylanilides and sulfonamides: An efficient method for the synthesis of 2-amidoindoles and indolo[1,2-a] quinazolines
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A Cu(I)-catalyzed, intermolecular protocol for the synthesis of 2-amidoindoles and tetrahydroindolo[1,2-a]quinazolines in shorter time and high yields is reported. The key highlight of this disclosure is the formation of 2-amidoindole and tetrahydroindolo[1,2-a]quinazoline moieties directly from gem-dibromovinylanilides and sulfonamides in a one-pot fashion through the in situ formation of ynamides followed by a base-promoted intramolecular hydroamidation.
- Kiruthika, Selvarangam E.,Perumal, Paramasivan Thirumalai
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p. 484 - 487
(2014/04/03)
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- Synthesis of pyrrolo-/indolo[1,2-a ]quinolines and naphtho[2,1- b ]thiophenes from gem -dibromovinyls and sulphonamides
-
A highly efficient and simple route for the synthesis of pyrrolo-/indolo[1,2-a]quinolines and naphtho[2,1-b]thiophenes from gem-dibromovinyls and sulphonamides is reported. The noteworthy feature of this report is that the methodology involves a two-step protocol to synthesize tri- and tetracyclic heterocycles in a one-pot fashion through the Cu(I)-catalyzed formation of ynamide followed by a Ag(I)-assisted intramolecular hydroarylation. The photophysical properties of representative examples of pyrrolo- and indolo[1,2-a]quinolines in solid and solution states have also been studied.
- Kiruthika, Selvarangam E.,Nandakumar, Avanashiappan,Perumal, Paramasivan Thirumalai
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p. 4424 - 4427
(2015/02/05)
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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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- Palladium-catalyzed benzylation of arylboronic acids with N,N-ditosylbenzylamines
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The palladium-catalyzed coupling of N,N-ditosylbenzylamines with arylboronic acids has been investigated, and the resulting diarylmethanes were obtained in high yields. Conversion of the amine to a N,N-ditosylimide group provided an efficient leaving group for the Pd-catalyzed benzylation of arylboronic acids.
- Yoon, Sangeun,Hong, Myeng Chan,Rhee, Hakjune
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p. 4206 - 4211
(2014/05/20)
-
- Tris(acetylacetonato)rhodium(III)-catalyzed α-alkylation of ketones, β-alkylation of secondary alcohols and alkylation of amines with primary alcohols
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The tris(acetylacetonato)rhodium(III) catalyst is shown to be a versatile catalyst in the presence of DABCO (1,4-diazabicyclo[2.2.2]octane) as ligand for the α-alkylation of ketones followed by transfer hydrogenation, for the one-pot β-alkylation of secondary alcohols with primary alcohols and for the alkylation of aromatic amines in the presence of an inorganic base in toluene. Copyright
- Satyanarayana, Ponnam,Reddy, Ganapam Manohar,Maheswaran, Hariharasharma,Kantam, Mannepalli Lakshmi
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supporting information
p. 1859 - 1867
(2013/07/19)
-
- The direct reductive amination of electron-deficient amines with aldehydes: The unique reactivity of the Re2O7 catalyst
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An unprecedented direct reductive amination of electron-deficient amines such as Cbz-, Boc-, EtOCO-, Fmoc-, Bz-, ArSO2-, Ar2PO-, etc. protected amines with aldehydes is achieved using the Re2O 7 catalyst and silanes as the hydride source. Excellent regioselective mono-alkylation and chemoselective reductive-amination were observed.
- Das, Braja Gopal,Ghorai, Prasanta
-
supporting information; experimental part
p. 8276 - 8278
(2012/09/22)
-
- Palladium-catalyzed N-alkylation of amides and amines with alcohols employing the aerobic relay race methodology
-
Possibly because homogeneous palladium catalysts are not typical borrowing hydrogen catalysts and ligands are thus ineffective in catalyst activation under conventional anaerobic conditions, they had not been used in the N-alkylation reactions of amines/amides with alcohols in the past. By employing the aerobic relay race methodology with Pd-catalyzed aerobic alcohol oxidation being a more effective protocol for alcohol activation, ligand-free homogeneous palladiums are successfully used as active catalysts in the dehydrative N-alkylation reactions, giving high yields and selectivities of the alkylated amides and amines. Mechanistic studies implied that the reaction most probably proceeds via the novel relay race mechanism we recently discovered and proposed. By employing the aerobic relay race methodology with Pd-catalyzed aerobic alcohol oxidation being a more effective protocol for alcohol activation, ligand-free homogeneous palladiums are successfully used as active catalysts in the dehydrative N-alkylation reactions of amines and amides with alcohols, giving high yields and selectivities of the alkylated amines and amides. Mechanistic studies implied that the reaction most probably proceeds via the novel relay race mechanism we recently discovered and proposed. Copyright
- Yu, Xiaochun,Jiang, Lan,Li, Qiang,Xu, Qing,Xie, Yuanyuan
-
p. 2322 - 2332,11
(2020/09/16)
-
- Cross-coupling of grignard reagents with sulfonyl-activated sp3 carbon-nitrogen bonds
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Sulfonyl-activated sp3 carbon-nitrogen bonds have been found to be cleaved by Grignard reagents in the presence of 5 mol% of copper(I) iodide (CuI). Significantly, a broad range of sulfonyl-activated benzylic, allylic, and propargylic amines smoothly undergo the cross-coupling reaction with Grignard reagents to afford structurally diverse coupling products in good to excellent yields and with high chemo-, regio-, and stereoselectivity. Moreover, an S N2 mechanism has been demonstrated to be involved in the cross-coupling reaction that allows the asymmetric synthesis of chiral hydrocarbons from optically active α-branched amine derivatives. Copyright
- Li, Man-Bo,Tang, Xiang-Ling,Tian, Shi-Kai
-
scheme or table
p. 1980 - 1984
(2011/10/12)
-
- Synthesis and cross-coupling of sulfonamidomethyltrifluoroborates
-
Sulfonamidomethyltrifluoroborates were successfully synthesized and cross-coupled with a wide range of aryl and heteroaryl chlorides, allowing the construction of a sulfonamidomethyl aryl linkage through a new disconnection, thus offering a new way to acc
- Molander, Gary A.,Fleury-Bregeot, Nicolas,Hiebel, Marie-Aude
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p. 1694 - 1697
(2011/05/04)
-
- Palladium(II) acetate as catalyst for the N-alkylation of aromatic amines, sulfonamides, and related nitrogenated compounds with alcohols by a hydrogen autotransfer process
-
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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- Rhodium-catalyzed aerobic N-alkylation of sulfonamides with alcohols
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By using the famous Wilkinson's catalyst, N-alkylation of sulfonamides can be easily realized under mild aerobic conditions by using alcohols as the alkylating reagent, giving monoalkylated sulfonamides in high yields and selectivities with water produced as the only byproduct. This advantageous aerobic method is potentially general in substrate scope that it can also be applied to other amides, amines and alcohols.
- Feng, Sun Lin,Liu, Chuan Zhi,Li, Qiang,Yu, Xiao Chun,Xu, Qing
-
scheme or table
p. 1021 - 1024
(2012/06/01)
-
- N-Alkylation of poor nucleophilic amines and derivatives with alcohols by a hydrogen autotransfer process catalyzed by copper(II) acetate: Scope and mechanistic considerations
-
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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- 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
-
supporting information; experimental part
p. 1336 - 1339
(2010/06/15)
-
- Catalytic coupling of N-benzylic sulfonamides with silylated nucleophiles at room temperature
-
In the presence of 2-10 mol% of Tf2NH, a range of N-benzylic sulfonamides smoothly react with allylic, propargylic, benzylic, or hydrido silanes at room temperature via sp3 carbon-nitrogen bond cleavage to afford structurally diverse products in moderate to excellent yields and with high chemo- and regioselectivity.
- Yang, Bai-Ling,Tian, Shi-Kai
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supporting information; experimental part
p. 6180 - 6182
(2010/10/20)
-
- Copper-catalyzed N-alkylation of sulfonamides with benzylic alcohols: Catalysis and mechanistic studies
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The N-alkylation of sulfonamides with alcohols is efficiently performed in the presence of easily available copper catalysts via hydrogen borrowing methodology. Applying a copper acetate/potassium carbonate system the reaction of sulfonamides and alcohols gave the corresponding secondary amines in excellent yield. In situ HR-MS analysis indicated that bissulfonylated amines are formed under air atmosphere, which act as self-stabilizing Iigands for the catalytic system. UV-visible measurements suggest the interaction between the copper centre and the bissulfonylated amine. Reactions of benzyl alcohol-d 7 with p-toluenesulfonamide, Nbenzyl-p-toluenesulfonamide or N-benzylidenetoluenesulfonamide revealed that the reaction proceeds via a transfer hydrogenation mechanism and the whole process is micro-reversible. Competitive reactions of benzyl alcohol and benzyl alconol-d7 with ptoluenesulfonamide revealed a kinetic isotope effect (kH/kD) of 3.287 (0.192) for the dehydrogenation of benzyl alcohol and 0.611 (0.033) for the hydrogenation of the N-benzylidene-p-toluenesulfonamide intermediate, which suggests that dehydrogenation of the alcohol is the rate-determining step.
- Cui, Xinjiang,Shi, Feng,Tse, Man Kin,Goerdes, Dirk,Thurow, Kerstin,Beller, Matthias,Deng, Youquan
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scheme or table
p. 2949 - 2958
(2010/03/24)
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- Selective benzylic and allylic alkylation of protic nucleophiles with sulfonamides through double Lewis acid catalyzed cleavage of sp3 carbon-nitrogen bonds
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The acid-catalyzed benzylic and allylic alkylation of protic nucleophiles is fundamentally important for the formation of carbon-carbon and carbon-heteroatom bonds, and it is a formidable challenge for benzylic and allylic amine derivatives to be used as the alkylating agents. Herein we report a highly efficient benzylic and allylic alkylation of protic carbon and sulfur nucleophiles with sulfonamides through double Lewis acid catalyzed cleavage of sp3 carbon-nitrogen bonds at room temperature. In the presence of a catalytic amount of inexpensive ZnCl2-TMSCl (TMSCl: chlorotrimethylsilane), 1,3-diketones, β-keto esters, β-keto amides, malononitrile, aromatic compounds, thiols, and thioacetic acid can couple with a broad range of tosylactivated benzylic and allylic amines to give diversely functionalized products in good to excellent yields and with high regioselectivity. Furthermore, the cross-coupling reaction of 1,3-dicarbonyl compounds with benzylic propargylic amine derivatives has been successfully applied to the one-step synthesis of polysubstituted furans and benzofurans.
- Liu, Cong-Rong,Li, Man-Bo,Yang, Cui-Feng,Tian, Shi-Kai
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supporting information; experimental part
p. 793 - 797
(2009/09/29)
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- Catalyst-free alkylation of sulfinic acids with sulfonamides via sp 3 C-N bond cleavage at room temperature
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An unprecedented catalyst-free alkylation of sulfinic acids with sulfonamides has been developed via sp3 C-N bond cleavage at room temperature. In the absence of external catalysts and additives, a wide variety of N-benzylic and N-allylic sulfonamides couple with sulfinic acids to give structurally diversified sulfones in moderate to excellent yields. Furthermore, the reaction of N-(2-acyl)allylic sulfonamides with sulfinic acids provides a convenient access to trisubstituted allyl sulfones with exclusive Z selectivity.
- Liu, Cong-Rong,Li, Man-Bo,Cheng, Dao-Juan,Yang, Cui-Feng,Tian, Shi-Kai
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supporting information; experimental part
p. 2543 - 2545
(2009/10/10)
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- One-step synthesis of substituted dihydro- and tetrahydroisoquinolines by FeCl3·6H2O catalyzed intramolecular Friedel-Crafts reaction of benzylamino-substituted propargylic alcohols
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(Chemical Equation Presented) A mild, versatile, and efficient method for the one-step synthesis of substituted dihydro- and tetrahydroisoquinolines has been developed by the FeCl3·6H2O catalyzed intramolecular allenylation/cyclization reaction of benzylamino-substituted propargylic alcohols, representing the first example of the intramolecular Friedel-Crafts reaction of propargylic alcohols.
- Huang, Wen,Shen, Quansheng,Wang, Jialiang,Zhou, Xigeng
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p. 1586 - 1589
(2008/09/17)
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- Synthesis of polymer-bound 4-acetoxy-3-phenylbenzaldehyde derivatives: Applications in solid-phase organic synthesis
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(Chemical Equation Presented) Aminomethyl polystyrene resin was reacted with 4-(5′-formyl-2′-hydroxyphenyl)benzoic acid and 4-(5′-formyl-2′-hydroxyphenyl)phenyl propionic acid, respectively, in the presence of 1-hydroxybenzotriazole and 1,3-diisopropylcarbodiimide to yield polymer-bound benzaldehydes. The phenolic group in resins was acetylated with acetic anhydride to afford two polymer-bound 4-acetoxybenzaldehydes. The reductive amination of polymer-bound linkers by amines and sodium triacetoxyborohydride, followed by sulfonylation with arylsulfonyl chloride derivatives in the presence of pyridine and the cleavage with TFA/DCM/H 2O, produced pure sulfonamides.
- Kumar, Anil,Ye, Guofeng,Ahmadibeni, Yousef,Parang, Keykavous
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p. 7915 - 7918
(2007/10/03)
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- An unexpected two-group migration involving a sulfonynamide to nitrile rearrangement. Mechanistic studies of a thermal N → C tosyl rearrangement
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(Chemical Equation Presented) We report the discovery of the first double-barreled thermal rearrangement of a sulfonynamide and a methoxybenzyl to a nitrite and the first rearrangement of an SO2 group from sulfonamide to ketoimine. The rearrang
- Bendikov, Michael,Duong, Hieu M.,Bolanos, Eduardo,Wudl, Fred
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p. 783 - 786
(2007/10/03)
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- Asymmetric Alkylation of N-Toluenesulfonylimines with Dialkylzinc Reagents Catalyzed by Copper-Chiral Amidophosphine
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The synthetic procedure of a chiral amidophosphine ligand 5 bearing two bulky substituents, 2,4,6-trimethylphenylmethyl or 2,4,6-triisopropylphenylmethyl groups, on the pyrrolidine ring was improved by employing the borane-THF reduction of the lactam-alco
- Soeta, Takahiro,Nagai, Kazushige,Fujihara, Hidetaka,Kuriyama, Masami,Tomioka, Kiyoshi
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p. 9723 - 9727
(2007/10/03)
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- A novel method for the synthesis of vicinal disulfonamides promoted by metallic samarium in aqueous media
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A new method to synthesize vicinal disulfonamides by reductive coupling of N-sulfonylimines in Sm/HCl/THF has been developed and various reaction conditions have been studied.
- Liu, Xi,Liu, Yunkui,Zhang, Yongmin
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p. 6787 - 6789
(2007/10/03)
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- Competitive Reaction Pathways in the Nucleophilic Substitution Reactions of Aryl Benzenesulfonates with Benzylamines in Acetonitrile
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The reactions of aryl benzenesulfonates (YC6H4SO2OC6H4Z) with benzylamines (XC6H4CH2NH2) in acetonitrile at 65.0 deg C have been studied. The reactons proceed competitevely by S-O (kS-O) and C-O (kC-O) bond scission, but the former provides the major reaction pathway. On the basis of analysis of the Hammet and Broensted coefficients together with the cross-interaction constants ρXY, ρYZ, and ρXZ, stepwise mechanisms are proposed in which the S-O bond cleavage proceeds by rate-limiting formation of a trigonal-bipyramidal pentacoordinate (TBP-5C) intermediate, whereas the C-O bond scission takes place by rate-limiting expulsion of the sulfonate anion (YC6H4SO3-) from a Meisenheimer-type complex.
- Choi, Jin Heui,Lee, Byung Choon,Lee, Hai Whang,Lee, Ikchoon
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p. 1277 - 1281
(2007/10/03)
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- p-Methoxybenzyl ether cleavage by polymer-supported sulfonamides.
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[reaction: see text] p-Methoxybenzyl ethers have been found to transfer from alcohols to sulfonamides in the presence of catalytic trifluoromethanesulfonic acid. This process for protecting group removal can be performed in solution with yields >94%. Through the use of sulfonamide-functionalized ("safety-catch") resins, p-methoxybenzyl ethers can be cleaved in excellent yields with minimal purification.
- Hinklin, Ronald J,Kiessling, Laura L
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p. 1131 - 1133
(2007/10/03)
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- Solid phase synthesis of sulfonamides using a carbamate linker
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A method for the synthesis of sulfonamides on a solid support by immobilizing amines through the nitrogen atom using a carbamate linkage is described.
- Raju,Kogan, Timothy P.
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p. 3373 - 3376
(2007/10/03)
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