- A Strategy to Control the Reactivation of Frustrated Lewis Pairs from Shelf-Stable Carbene Borane Complexes
-
N-Phosphine oxide substituted imidazolylidenes (PoxIms) have been synthesized and fully characterized. These species can undergo significant changes to the spatial environment surrounding their carbene center through rotation of the phosphine oxide moiety. Either classical Lewis adducts (CLAs) or frustrated Lewis pairs (FLPs) are thus formed with B(C6F5)3 depending on the orientation of the phosphine oxide group. A strategy to reactivate FLPs from CLAs by exploiting molecular motions that are responsive to external stimuli has therefore been developed. The reactivation conditions were successfully controlled by tuning the strain in the PoxIm-B(C6F5)3 complexes so that reactivation only occurred above ambient temperature. Frustration under control: Imidazolylidenes with a phosphine oxide substituent on one of the nitrogen atoms can undergo drastic changes to the spatial environment surrounding their carbene center through rotation of the phosphine oxide moiety. Depending on the orientation of this group, either classical Lewis adducts or frustrated Lewis pairs (FLPs) are formed upon addition of B(C6F5)3.
- Hoshimoto, Yoichi,Kinoshita, Takuya,Ohashi, Masato,Ogoshi, Sensuke
-
-
Read Online
- 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)
-
- AEROBIC OXIDATIVE SYNTHESIS OF SULFONAMIDE USING Cu CATALYST
-
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.
- -
-
Paragraph 0033-0037; 0039-0054; 0129-0131
(2021/04/06)
-
- Synthetic method for catalyzing imine to be reduced into amine
-
The invention discloses a synthesis method for catalyzing imine to be reduced into amine, wherein the synthesis method is characterized by comprising the following steps: 1, sequentially putting a sulfonyl imine compound and a catalyst I into a reaction bottle according to a reaction molar ratio of 1:0.01 at normal temperature and normal pressure, adding formic acid and a triethylamine solution according to a volume ratio of 5:2, and reacting in a solvent for 1-15 minutes to obtain a reaction product; and 2, after the reaction in the step 1 is finished, sequentially and slowly adding water and ethyl acetate into an obtained reaction product, sufficiently stirring, standing for layering, extracting a separated water layer by using ethyl acetate, combining an extract of ethyl acetate with a separated organic layer, washing by using saturated edible salt water, and drying by using anhydrous sodium sulfate, evaporating to remove the ethyl acetate solvent to obtain a crude product, and separating and purifying by silica gel column chromatography to obtain the amine compound.
- -
-
Paragraph 0076-0078
(2021/04/14)
-
- Implication of a Silyl Cobalt Dihydride Complex as a Useful Catalyst for the Hydrosilylation of Imines
-
Here, we describe the formation and use of silyl cobalt (III) dihydride complexes as powerful catalysts for the hydrosilylation of a variety of imines starting from a low-valent well-defined cobalt (I) complex. The reaction is efficient at low catalyst loadings with a diverse range of imines bearing various protecting groups, as well as aliphatic ketimines and quinoline. Kinetics, DFT calculations, NMR spectroscopic studies, deuteration experiments, and X-ray diffraction analyses allowed us to propose a catalytic cycle based on silyl dihydrocobalt (III) complexes performing a hydrocobaltation.
- Barbazanges, Marion,Bories, Cassandre C.,Derat, Etienne,Petit, Marc
-
p. 14262 - 14273
(2021/11/27)
-
- Amide Iridium Complexes As Catalysts for Transfer Hydrogenation Reduction of N-sulfonylimine
-
Sulfonamide moieties widely exist in natural products, biologically active substance, and pharmaceuticals. Here, an efficient water-soluble amide iridium complexes-catalyzed transfer hydrogenation reduction of N-sulfonylimine is developed, which can be carried out under environmentally friendly conditions, affording a series of sulfonamide compounds in excellent yields (96-98%). In comparison with organic solvents, water is shown to be critical for a high catalytic transfer hydrogenation reduction in which the catalyst loading can be as low as 0.001 mol %. These amide iridium complexes are easy to synthesize, one structure of which was determined by single-crystal X-ray diffraction. This protocol gives an operationally simple, practical, and environmentally friendly strategy for synthesis of sulfonamide compounds.
- Wen, Huiling,Luo, Nianhua,Zhu, Qianheng,Luo, Renshi
-
p. 3850 - 3859
(2021/03/09)
-
- Preparation method of nitrogen-substituted sulfonamide compound
-
The invention discloses a preparation method of a nitrogen-substituted sulfonamide compound, and belongs to the field of organic synthesis. The nitrogen-substituted sulfonamide compound as shown in aformula (I) is prepared by directly coupling an aryl sulfonamide compound as shown in a formula (II) and a p-toluenesulfonylhydrazone compound as shown in a formula (III) under the action of a specific copper catalyst, an alkali reagent and an additive without ligand participation and a high-temperature reaction system. According to the method, the raw materials are cheap and easy to obtain, the reaction process is green, simple and convenient, and the yield of the nitrogen-substituted sulfonamide compound can reach 76%.
- -
-
Paragraph 0031-0038
(2020/04/02)
-
- 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.
-
supporting information
p. 5262 - 5266
(2020/09/17)
-
- Cyanide-Mediated Synthesis of Sulfones and Sulfonamides from Vinyl Sulfones
-
We report a facile synthesis of sulfones, β-keto sulfones, and sulfonamides from vinyl sulfones via an addition-elimination sequence where in situ generation of nucleophilic sulfinate ion is mediated by cyanide. The use vinyl sulfones renders high selectivity for S -alkylation to produce sulfones in high yields. In the presence of N -bromosuccinimide, primary and secondary amines underwent sulfonamide formation. A preliminary mechanistic study showed the formation of acrylonitrile as an innocent byproduct, without interfering with the desired reaction pathway while generating a sulfinate nucleophile.
- Lee, Ji-Woong,Roy, Tamal
-
p. 455 - 458
(2020/03/13)
-
- Efficient and Practical Synthesis of Sulfonamides Utilizing SO2 Gas Generated on Demand
-
A simple and practical protocol was developed for the synthesis of sulfonamides by reacting organometallic reagents with SO2 gas generated on demand. SO2 was generated from readily available reagents safely in a highly contained and controlled fashion. The protocol allows the synthesis of sulfonamides without using either atom-inefficient SO2 surrogates or a SO2 cylinder that requires stringent storage regulations in the laboratory. The protocol was successfully applied to the synthesis of sildenafil.
- Chung Leung, Gulice Yiu,Ramalingam, Balamurugan,Loh, Gabriel,Chen, Anqi
-
p. 546 - 554
(2020/04/22)
-
- Synthesis of sulfonamides promoted by alkyl iodide via a hypervalent iodine intermediate
-
A new method for the preparation of sulfonamides from sodium sulfinates and amines is developed. A stoichiometric amount of m-chloroperbenzoic acid as oxidant and a catalytic amount of 1-iodopropane provides the corresponding sulfonamides in good yields under mild reaction conditions. In this protocol, 1-iodopropane is first oxidized by m-chloroperbenzoic acid into the corresponding hypervalent iodine intermediate iodosylpropane, which is highly unstable and decomposes at once to form hypoiodous acid. Then, the following reaction of the generated active hypoiodous acid with sodium sulfinates and amines results in the corresponding sulfonamides.
- Zhou, Zhongshi,He, Xuehan
-
supporting information
p. 280 - 284
(2019/11/16)
-
- Method for synthesizing N-alkyl sulfonamide in water
-
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 0128; 0129; 0130; 0131; 0132
(2020/12/30)
-
- Hypervalent Iodine Mediated Sulfonamide Synthesis
-
A new metal-free sulfonylation reaction is described. The method takes advantage of the Umpolung reactivity and group-transfer properties of iodine(III) compounds, combining hypervalent iodine reagents and sulfinate salts to deliver a clean and mild transfer of sulfonyl groups to amines and anilines. A total of 25 sulfonamides was synthesised in up to 99 % yield, even on gram-scale. The reaction mechanism was investigated by ESI-MS and DFT calculations.
- Poeira, Diogo L.,Macara, Jo?o,Faustino, Hélio,Coelho, Jaime A. S.,Gois, Pedro M. P.,Marques, M. Manuel B.
-
supporting information
p. 2695 - 2701
(2019/04/08)
-
- Cu-catalyzed aerobic oxidative synthesis of sulfonamides from sulfonyl hydrazides and amines
-
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
-
supporting information
p. 792 - 795
(2019/02/16)
-
- Sulfonamide Synthesis through Electrochemical Oxidative Coupling of Amines and Thiols
-
Sulfonamides are key motifs in pharmaceuticals and agrochemicals, spurring the continuous development of novel and efficient synthetic methods to access these functional groups. Herein, we report an environmentally benign electrochemical method which enables the oxidative coupling between thiols and amines, two readily available and inexpensive commodity chemicals. The transformation is completely driven by electricity, does not require any sacrificial reagent or additional catalysts and can be carried out in only 5 min. Hydrogen is formed as a benign byproduct at the counter electrode. Owing to the mild reaction conditions, the reaction displays a broad substrate scope and functional group compatibility.
- Laudadio, Gabriele,Barmpoutsis, Efstathios,Schotten, Christiane,Struik, Lisa,Govaerts, Sebastian,Browne, Duncan L.,No?l, Timothy
-
supporting information
(2019/04/16)
-
- Sulfonamide Synthesis through Electrochemical Oxidative Coupling of Amines and Thiols
-
Sulfonamides are key motifs in pharmaceuticals and agrochemicals, spurring the continuous development of novel and efficient synthetic methods to access these functional groups. Herein, we report an environmentally benign electrochemical method which enables the oxidative coupling between thiols and amines, two readily available and inexpensive commodity chemicals. The transformation is completely driven by electricity, does not require any sacrificial reagent or additional catalysts and can be carried out in only 5 min. Hydrogen is formed as a benign byproduct at the counter electrode. Owing to the mild reaction conditions, the reaction displays a broad substrate scope and functional group compatibility.
- Laudadio, Gabriele,Barmpoutsis, Efstathios,Schotten, Christiane,Struik, Lisa,Govaerts, Sebastian,Browne, Duncan L.,No?l, Timothy
-
supporting information
p. 5664 - 5668
(2019/04/17)
-
- 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
-
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
-
p. 10755 - 10762
(2019/07/15)
-
- Plasma-Made (Ni0.5Cu0.5)Fe2O4 Nanoparticles for Alcohol Amination under Microwave Heating
-
Amine N-alkylation is a process involved in the production of a wide range of chemicals. Here we describe the synthesis of well-defined (Ni0.5Cu0.5)Fe2O4 magnetic nanoparticles by plasma induction, and their successful application to amine N-alkylation using alcohols as coupling agents through a borrowing hydrogen pathway. Plasma induction allows precise morphology and size control over nanoparticle synthesis, while allowing the one-pot production of decagram quantities of material. Up to date, such nanoparticles have never been applied for organic reactions. By coupling high-end characterization techniques with catalytic optimization, we showed that small Cu(0) satellite nanoparticles played an essential role in alcohol oxidation, whereas both Ni and Cu were required for the last step of the reaction. Using elemental mapping, we demonstrated that catalyst deactivation occurred through a leaching/re-deposition mechanism of Cu and Ni. The reactions were conducted under microwave conditions, which exerted a positive effect on catalytic activity. Finally, the catalyst was active at low metal loadings (2 mol%) even on the gram-scale, and affording unprecedented TON for this reaction catalyzed by Ni/Cu bimetallic systems (19).
- Li, Alain You,Dumaresq, Nicolas,Segalla, Andréanne,Braidy, Nadi,Moores, Audrey
-
p. 3959 - 3972
(2019/08/12)
-
- Manganese-Catalyzed N-Alkylation of Sulfonamides Using Alcohols
-
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.
-
p. 3715 - 3724
(2019/03/30)
-
- Enantioselective Synthesis of trans-Vicinal Diamines via Rhodium-Catalyzed [2+2] Cycloaddition of Allenamides
-
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)
-
- Synthesis of CF3CH2-Containing Indolines by Transition-Metal-Free Aryltrifluoromethylation of Unactivated Alkenes
-
With an unactivated double bond as the radical acceptor, allyl amines underwent a metal-free trifluoromethylation/cyclization cascade with CF3SO2Na (Langlois' reagent), affording CF3CH2-containing indolines and tetrahydroisoquinolines, whose practical syntheses are significant challenges. This protocol features mild conditions, low cost, and a broad substrate scope.
- Liang, Deqiang,Dong, Qishan,Xu, Penghui,Dong, Ying,Li, Weili,Ma, Yinhai
-
supporting information
p. 11978 - 11986
(2018/09/27)
-
- MANUFACTURING METHOD OF COMPOUND HAVING SULFONYL GROUP
-
The present invention relates to a method for manufacturing a compound having a sulfonyl group, which includes a step for reacting thiosulfonates in a solvent comprising nucleophilic bases with an electrophilic agent. Accordingly, the present invention can manufacture the compound having the sulfonyl group with a variety of structures with high efficiency and high yield through more simplified processes than conventional methods.COPYRIGHT KIPO 2018
- -
-
Paragraph 0187; 0188; 0190-0193
(2018/10/03)
-
- Selective cleavage of the N-propargyl group from sulfonamides and amides under ruthenium catalysis
-
The selective cleavage of the N-propargyl group from sulfonamides and amides under ruthenium catalysis is described. The reaction tolerates a broad range of functional groups, and the desired products were obtained in 10–95% yield.
- Wang, Jingjing,Li, Feng,Pei, Wenlong,Yang, Mixue,Wu, Yidan,Ma, Danyang,Zhang, Furong,Wang, Jianhui
-
supporting information
p. 1902 - 1905
(2018/04/19)
-
- Highly Efficient Copper-Catalyzed Amidation of Benzylic Hydrocarbons Under Neutral Conditions
-
A ligand free method has been developed for the amidation of benzylic hydrocarbons. A range of benzylic amides has been prepared with the use of dicumyl peroxide and a copper catalyst in good to excellent yields.
- Howard, Eva-Louise,Guzzardi, Norman,Tsanova, Viliyana G.,Stika, Angeliki,Patel, Bhaven
-
supporting information
p. 794 - 797
(2018/02/21)
-
- PTAB mediated open air synthesis of sulfonamides, thiosulfonates and symmetrical disulfanes
-
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
-
supporting information
p. 2360 - 2364
(2018/05/24)
-
- NaI-Catalyzed Oxidative Amination of Aromatic Sodium Sulfinates: Synergetic Effect of Ethylene Dibromide and Air as Oxidants
-
A novel NaI-catalyzed oxidative amination of sodium sulfinates, employing both ethylene dibromide (EDB) and air as the oxidants, is described. EDB was first demonstrated to be a promising mild organic oxidant that in air, converted NaI into molecular iodine to promote the cross-coupling reactions of aromatic sodium sulfinates with amines to produce arylsulfonamides. Mechanistic studies indicated that a radical pathway might be involved in the reaction process.
- Fu, Ying,Li, Quan-Zhou,Xu, Qin-Shan,Hügel, Helmut,Li, Ming-Peng,Du, Zhengyin
-
supporting information
p. 6966 - 6970
(2018/11/23)
-
- Method for catalytic synthesis of N-benzyl benzene sulfonamide compounds by boric acid/oxalic acid catalytic system under microwave radiation
-
The invention discloses a method for catalytic synthesis of N-benzyl benzene sulfonamide compounds by a boric acid/oxalic acid catalytic system under microwave radiation. The method includes: adoptingbenzyl alcohol and derivatives thereof and benzene sulfonamide derivatives as raw materials, adopting the boric acid/oxalic acid system as a catalyst, and adopting fluorobenzene as a solvent; performing reaction in a microwave reactor under certain temperature and power conditions, performing vacuum concentration after reaction for a period of time, and subjecting a product to column chromatographic purification to realize efficient catalytic preparation of the N-benzyl benzene sulfonamide compounds. Compared with the prior art, the method has advantages of evidently higher reaction speed than that of conventional heating, mild reaction conditions, simplicity in operation, high yield, safety, low cost and environmental friendliness.
- -
-
Paragraph 0031; 0086-0091
(2018/09/11)
-
- Versatile and green synthesis, spectroscopic characterizations, crystal structure and DFT calculations of 1,2,3?triazole?based sulfonamides
-
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
-
-
- Efficient synthesis of novel 1,3-diyne-based sulfonamides using CuCl2/Et3N as a robust catalytic system
-
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
-
p. 188 - 194
(2017/03/07)
-
- A segmented flow platform for on-demand medicinal chemistry and compound synthesis in oscillating droplets
-
We report an automated flow chemistry platform that can efficiently perform a wide range of chemistries, including single/multi-phase and single/multi-step, with a reaction volume of just 14 μL. The breadth of compatible chemistries is successfully demonstrated and the desired products are characterized, isolated, and collected online by preparative HPLC/MS/ELSD.
- Hwang, Ye-Jin,Coley, Connor W.,Abolhasani, Milad,Marzinzik, Andreas L.,Koch, Guido,Spanka, Carsten,Lehmann, Hansjoerg,Jensen, Klavs F.
-
p. 6649 - 6652
(2017/07/10)
-
- Synthesis process of sulfonamide compounds in microwave system
-
The invention discloses a synthesis process of sulfonamide compounds in a microwave system. The synthesis process is realized by the following steps: by using CuCl as a catalyst and FeCl3 as an oxidant, carrying out carbon-hydrogen activating and carbon-nitrogen coupling reaction in a DMF (Dimethyl Formamide) by substituting sulfanilamide and methylbenzene through microwave heating and efficient catalysis for 10 to 60 minutes; extracting a product by using ethyl acetate; carrying out vacuum concentration; carrying out column chromatographic purification on a product to obtain the sulfonamide compounds. The synthesis process is a method for efficiently preparing the sulfonamide compounds, which is environment-friendly and is simple and convenient to operate. Compared with the prior art, the synthetic process disclosed by the invention has the advantages of remarkably-increased reaction speed compared with that under a conventional heating condition, mild reaction conditions, simple operation, high yield, safety, low cost and environmental protection.
- -
-
Paragraph 0007; 0021; 0032
(2017/08/14)
-
- A Route to O-Aminosulfonates and Sulfonamides through Insertion of Sulfur Dioxide and Hydrogen Atom Transfer
-
A three-component reaction of aryldiazonium tetrafluoroborates, the 1,4-diazabicyclo[2.2.2]octane?bis(sulfur dioxide) adduct [DABCO?(SO2)2] and hydroxylamines under catalyst-free and additive-free conditions has been developed, providing aryl O-aminosulfonates in good yields. Sulfonamides could also be obtained via a one-pot process through the reaction of aryldiazonium tetrafluoroborates, DABCO?(SO2)2 and amines in the presence of N-hydroxybenzotriazole. A mechanism involving the insertion of sulfur dioxide and hydrogen atom transfer is proposed and supported by theoretical calculations. (Figure presented.).
- Liu, Tong,Zheng, Danqing,Li, Zhenhua,Wu, Jie
-
supporting information
p. 2653 - 2659
(2017/08/16)
-
- Nondirected, cu-catalyzed sp3 C-H aminations with hydroxylamine-based amination reagents: Catalytic and mechanistic studies
-
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.
-
p. 1259 - 1268
(2017/05/29)
-
- Synthesis of Sulfones and Sulfonamides via Sulfinate Anions: Revisiting the Utility of Thiosulfonates
-
Simple and high-yielding strategies for the production of a variety of sulfones and sulfonamides, using thiosulfonates synthesized by copper-catalyzed aerobic dimerization, are reported. Although thiosulfonates are an old class of compound, practical methods for their synthesis and utilization have not been rigorously developed. In this study, we revisit the reactions of easily accessible thiosulfonates to form sulfinate anions. Because of the similar reactivity of thiosulfonates and metal sulfinates derived from toxic SO2, thiosulfinates are proposed to be stable, nontoxic alternatives to metal sulfinate salts.
- Shyam, Pranab K.,Jang, Hye-Young
-
p. 1761 - 1767
(2017/02/10)
-
- Copper-Catalyzed Sulfonylation of Alkenes and Amines by Using Thiosulfonates as a Sulfonylating Agent
-
Synthetically and pharmaceutically useful vinyl sulfones and sulfonamides are synthesized by the direct coupling of thiosulfonates with alkenes and amines, respectively. Copper catalysts help to generate the sulfonyl group from thiosulfonates and to form the C(sp2)–S/N–S bonds of the organosulfur compounds. This paper discusses the scope of these reactions of aromatic and aliphatic thiosulfonates with alkenes and amines.
- Shyam, Pranab K.,Son, Soobin,Jang, Hye-Young
-
p. 5025 - 5031
(2017/09/22)
-
- Nickel-catalyzed product-controllable amidation and imidation of sp3 C-H bonds in substituted toluenes with sulfonamides
-
A nickel-catalyzed product-controllable imidation and amidation of sp3 C-H bonds in substituted toluenes with sulfonamides were developed. Based on the change of the reaction time and atmosphere from N2 to O2, this reaction proceeded in high yields and excellent selectivity under different conditions. Mechanistic details were also described.
- Li, Ze-lin,Jin, Li-kun,Cai, Chun
-
supporting information
p. 1317 - 1320
(2017/02/15)
-
- Diamination of Domino Aryne Precursor with Sulfonamides
-
The reaction of a domino aryne precursor with sulfonamides efficiently afforded both 1,3-diaminobenzenes and trisubstituted 1,3-diaminobenzenes by simply varying the reaction conditions. Mechanistic study supports the sequential formation of two transient aryne intermediates involved in the reaction.
- Qiu, Dachuan,He, Jia,Yue, Xiao,Shi, Jiarong,Li, Yang
-
supporting information
p. 3130 - 3133
(2016/07/14)
-
- UV Light Induced Direct Synthesis of Phenanthrene Derivatives from a Linear 3-Aryl-N-(arylsulfonyl) Propiolamides
-
A novel photochemical approach for the synthesis of phenanthrene derivatives from linear 3-aryl-N-(arylsulfonyl) propiolamides via a tandem radical Smiles rearrangement/C-S bonding/Mallory reaction is disclosed. The control experiment results and isolation of the key intermediates give further insight into the reaction mechanism. Gram scale reaction using a flow reactor demonstrated the synthetic potential applications of our protocol.
- Chen, Ming,Yang, Chao,Wang, Yanpei,Li, Dazhi,Xia, Wujiong
-
supporting information
p. 2280 - 2283
(2016/06/01)
-
- Visible Light-Induced Radical Rearrangement to Construct C-C Bonds via an Intramolecular Aryl Migration/Desulfonylation Process
-
A highly efficient intramolecular selective aryl migration/desulfonylation of 2-bromo-N-aryl-N-(arenesulfonyl)amide via visible light-induced photoredox catalysis has been accomplished. This approach allows for the construction of a variety of multisubstituted N,2-diarylacetamide under mild reaction conditions.
- Li, Yuyuan,Hu, Bei,Dong, Wuheng,Xie, Xiaomin,Wan, Jun,Zhang, Zhaoguo
-
p. 7036 - 7041
(2016/08/30)
-
- Amidation via ligand-free direct oxidative C(sp3)-H/N[sbnd]H coupling with Cu-CPO-27 metal-organic framework as a recyclable heterogeneous catalyst
-
A copper-based metal-organic framework Cu-CPO-27 was synthesized, and used as a recyclable catalyst for the amidation of unactivated alkanes by benzamides via direct oxidative C(sp3)-H/N[sbnd]H coupling under ligand-free conditions. Using a catalytic amount of the Cu-CPO-27 for the transformation, high yields of N-cyclohexyl benzamides were achieved. The Cu-CPO-27 was more catalytically active than other Cu-MOFs such as Cu3(BTC)2, Cu(BDC), Cu(EDB), Cu2(BPDC)2(BPY), Cu2(BDC)2(DABCO), and Cu2(EDB)2(BPY). The Cu-CPO-27 also exhibited advantages as compared to several copper-based salts, including Cu(OAc)2, CuCl2, CuBr, CuI, CuCl, Cu(NO3)2, and CuSO4. The Cu-CPO-27 catalyst could be reused several times for the amidation transformation while its catalytic activity was not decreased significantly. To the best of our knowledge, the amidation of unactivated alkanes by benzamides via direct oxidative C(sp3)-H/N[sbnd]H coupling was not previously performed under heterogeneous catalysis conditions.
- Hoang, Thanh T.,Nguyen, Hanh T.H.,Le, Tien T.,Le, Dung T.,Truong, Thanh,Phan, Nam T.S.
-
p. 8241 - 8251
(2016/11/23)
-
- Copper-Catalyzed Enantioselective Addition of Styrene-Derived Nucleophiles to Imines Enabled by Ligand-Controlled Chemoselective Hydrocupration
-
The copper-catalyzed intermolecular enantioselective addition of styrenes to imines has been achieved under mild conditions at ambient temperature. This process features the use of styrenes as latent carbanion equivalents via the intermediacy of catalytically generated benzylcopper derivatives, providing an effective means for accessing highly enantiomerically enriched amines bearing contiguous stereocenters. Mechanistic studies shed light on the origin of the preferential styrene hydrocupration in the presence of an imine with the Ph-BPE-derived copper catalyst.
- Yang, Yang,Perry, Ian B.,Buchwald, Stephen L.
-
supporting information
p. 9787 - 9790
(2016/08/19)
-
- One-Pot Synthesis of Sulfonamides from Sodium Sulfinates and Amines via Sulfonyl Bromides
-
a new and convenient procedure has been developed for the preparation of sulfonamides from sodium sulfinates and amines with (n-C4H9)4NBr as bromine source and m-chloroperbenzoic acid as oxidant. This S-N bond formation reaction proceeds efficiently via sulfonyl bromides under neutral conditions to afford the corresponding sulfonamides in good yields at room temperature.
- Wu, Sixue,Zhang, Yikun,Zhu, Min,Yan, Jie
-
p. 2699 - 2704
(2016/11/30)
-
- 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 0163-0166
(2016/10/10)
-
- Re-entry of tin in N-alkylation: First example of a homogeneous heterobimetallic Pd-Sn catalyst for base and additive free alkylation of amine and surrogates with alcohol
-
The N-alkylation of amines, and amides with benzyl alcohols is catalyzed by bimetallic catalyst [Pd(COD)(SnCl3)Cl] in o-xylene. The reaction does not require additional base, additive or ligand, and is insensitive toward air and moisture and involves minimal work-up. These features make the reaction attractive, simple, and practical.
- Mohanty, Anuradha,Roy, Sujit
-
supporting information
p. 2749 - 2753
(2016/06/09)
-
- Efficient and practical catalyst-free-like dehydrative N-alkylation of amines and sulfinamides with alcohols initiated by aerobic oxidation of alcohols under air
-
We developed simple and practical N-alkylation reactions of amines and sulfinamides with primary and secondary alcohols by using only catalytic amounts of air as the initiator without adding any external catalysts. This method has advantages of simple conditions, easy operation, and comparatively wider scope of substrates, providing an efficient and green catalyst-free-like alcohol-based dehydrative N-alkylation method. Mechanistic studies revealed that air initiated the reactions by aerobic oxidation of the alcohols to the key initiating aldehydes or ketones in the presence of bases.
- Li, Xiaohui,Li, Shuangyan,Li, Qiang,Dong, Xu,Li, Yang,Yu, Xiaochun,Xu, Qing
-
supporting information
p. 264 - 272
(2015/12/30)
-
- Selective catalytic Hofmann: N -alkylation of poor nucleophilic amines and amides with catalytic amounts of alkyl halides
-
Using only catalytic amounts of alkyl halides in the reactions of poor nucleophilic amines/amides and alcohols led to a selective Hofmann N-alkylation reaction catalytic in alkyl halides, providing a practical and efficient method for the practical synthesis of mono- or di-alkylated amines/amides in high selectivities. This new method avoids the use of large amounts of bases, alkyl halides, and solvents, and generates water as the only byproduct. Preliminary mechanistic studies showed that alkyl halides are key intermediates/catalysts regeneratable in the reaction cycle.
- Xu, Qing,Xie, Huamei,Zhang, Er-Lei,Ma, Xiantao,Chen, Jianhui,Yu, Xiao-Chun,Li, Huan
-
supporting information
p. 3940 - 3944
(2016/07/21)
-
- Palladium-Catalyzed Regio- and Chemoselective Reactions of 2-Bromobenzyl Bromides: Expanding the Scope for the Synthesis of Biaryls Fused to a Seven-Membered Sultam
-
Speedy access to biaryls fused to seven-membered sultams was achieved by starting from readily accessible N-alkylbenzenesulfonamides and 2-bromobenzyl bromides. The protocol features a domino reaction and proceeds through an N-benzylation followed by an intramolecular direct C-H arylation that occurs ortho to the sulfonamide group. A palladium-catalyzed domino reaction of N-alkylbenzenesulfonamides and 2-bromobenzyl bromides gives biaryls fused to a seven-membered sultam. This approach employs readily accessible substrates and provides speedy access to fused-ring compounds.
- Laha, Joydev K.,Sharma, Shubhra,Dayal, Neetu
-
p. 7885 - 7891
(2015/12/24)
-
- Metal-free direct N-benzylation of sulfonamides with benzyl alcohols by employing boron trifluoride-diethyl ether complex
-
N-Benzylation of sulfonamides with both primary and secondary benzyl alcohols by employing boron trifluoride-diethyl ether complex under mild reaction conditions has been developed, which is an environmentally benign and facile protocol for assembling a series of primary and secondary benzyl sulfonamides in yields up to 83%. In this coupling reaction, the beneficial role of water has been clarified in detail through control experiments.
- Pan, Jing,Li, Jia-Qiang,Huang, Ruo-Feng,Zhang, Xiao-Hui,Shen, Hang,Xiong, Yan,Zhu, Xiang-Ming
-
supporting information
p. 1101 - 1108
(2015/04/14)
-
- Metal-free direct construction of sulfonamides via iodine- mediated coupling reaction of sodium sulfinates and amines at room temperature
-
A simple, practical, and metal-free protocol has been developed for the synthesis of sulfonamides from sodium sulfinates and various amines through an iodine-mediated SN bond formation reaction at room temperature. This green reaction is cost-effective, operationally straightforward, and especially proceeds under very mild conditions to afford the target products in good to excellent yields (up to 98%).
- Wei, Wei,Liu, Chunli,Yang, Daoshan,Wen, Jiangwei,You, Jinmao,Wang, Hua
-
supporting information
p. 987 - 992
(2015/03/30)
-