- Photolysis of p-Toluenesulfonyl Azide and Its Charge-Transfer Complex with Aniline
-
Photolysis of p-toluenesulfonyl azide (1) in p-xylene and cyclohexane gives primarily the products derived from insertion of (p-tolylsulfonyl)nitrene into the solvent.For p-xylene, an unstable intermediate product is formed which decomposes in the dark at room temperature to give both the ring-insertion product and the corresponding p-toluenesulfonamide (2).Photolysis of the ground-state charge-transfer complex between p-toluenesulfonyl azide and aniline gives six products, the major product being the sulfonyl hydrazide 7.Furthermore, formation of the insertion product by reaction with the solvent provides evidence for production of (p-tolylsulfonyl)nitrene from the excited charge-transfer complex.
- Hoyle, C. E.,Lenox, R. S.,Christie, P. A.,Shoemaker, R. A.
-
-
Read Online
- AgOTf catalyzed direct amination of benzyl alcohols with sulfonamides
-
AgOTf catalyzed direct amination of primary alcohols with sulfonamides is described. This effective catalyst requires no preactivation of the hydroxy group of alcohols and the reaction is environmentally benign with water as a by-product. Various primary alcohols on amination with sulfonamides gave the corresponding products in moderate to good yields.
- Sreedhar,Surendra Reddy,Amarnath Reddy,Neelima,Arundhathi
-
-
Read Online
- B(C6F5)3-catalyzed transfer hydrogenation of imines and related heteroarenes using cyclohexa-1,4-dienes as a dihydrogen source
-
The strong boron Lewis acid tris(pentafluorophenyl) borane, B(C6F5)3, is shown to abstract a hydride from suitably donor-substituted cyclohexa-1,4-dienes, eventually releasing dihydrogen. This process is coupled with the FLPtype (FLP = frustrated Lewis pair) hydrogenation of imines and nitrogen-containing heteroarenes that are catalyzed by the same Lewis acid. The net reaction is a B(C 6F5)3-catalyzed, i.e., transition-metal-free, transfer hydrogenation using easy-toaccess cyclohexa-1,4-dienes as reducing agents. Competing reaction pathways with or without the involvement of free dihydrogen are discussed.
- Chatterjee, Indranil,Oestreich, Martin
-
-
Read Online
- Electrosynthesis of Arylsulfonamides from Amines and Sodium Sulfinates Using H2O-NaI as the Electrolyte Solution at Room Temperature
-
With H2O as the solvent and NaI as the supporting electrolyte, a green and efficient electrochemical route has been developed to synthesize arylsulfonamides via I2electrogenerated in situ at a graphite anode to promote the reaction of sodium sulfinates with aromatic or aliphatic primary and secondary amines. The target products could be obtained in good to excellent yields at room temperature.
- Zhang, Chen,Chen, Yibin,Yuan, Gaoqing
-
-
Read Online
- Solid phase synthesis of sulfonamides using a carbamate linker
-
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.
-
-
Read Online
- Elimination of benzotriazolyl group in N-(α -benzotriazol-1-ylalkyl)amides and N-(α -benzotriazol-1-ylalkyl)sulfonamides: Their self-coupling and cross-coupling reactions with carbonyl compounds
-
The elimination of benzotriazolyl group from N-(α -benzotriazol-1-ylalkyl)amides and N-(α -benzotriazol-1-ylalkyl)sulfonamides are readily realized with samarium diiodide as a reducing agent. The resulting intermediates undergo a dimerization or cross-coupling reaction with carbonyl compounds, thus affording the corresponding dimers or α-hydroxyalkylated sulfonamides in moderate yields.
- Wang, Xiaoxia,Liu, Yongjun,Zhang, Yongmin
-
-
Read Online
- New reactivity of methoxyhydridosilane in the catalytic activation system
-
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
-
-
Read Online
- A novel method for the synthesis of vicinal disulfonamides promoted by metallic samarium in aqueous media
-
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
-
-
Read Online
- The effect of coordination on the reaction of N-tosyl imines with diethylzinc
-
The effect of coordination on the reaction of N-tosyl imines and diethylzinc was studied in detail. It showed that there was strong coordination between N-tosyl imine and diethylzinc. Due to this coordination, N-tosyl imines could be reduced directly thro
- Gao, Feifeng,Deng, Minzhi,Qian, Changtao
-
-
Read Online
- 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)
-
- Diiodine-Triethylsilane System: Reduction of N-Sulfonyl Aldimines to N-Alkylsulfonamides
-
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
-
supporting information
p. 291 - 294
(2020/11/09)
-
- Nickel/Photoredox Dual Catalytic Cross-Coupling of Alkyl and Amidyl Radicals to Construct C(sp3)-N Bonds
-
The construction of C(sp3)-N bonds via direct radical-radical cross-coupling under benign conditions is a desirable but challenging approach. Herein, the cross-coupling of alkyl and amidyl radicals to build aliphatic C-N bonds in a concise, mild, and oxid
- Zhou, Shaofang,Lv, Kang,Fu, Rui,Zhu, Changlei,Bao, Xiaoguang
-
p. 5026 - 5034
(2021/05/07)
-
- Copper-boryl mediated transfer hydrogenation of N-sulfonyl imines using methanol as the hydrogen donor
-
B2Pin2-assisted copper-catalyzed transfer hydrogenation of aromatic sulfonylimines has been achieved, delivering a variety of aryl/heteroaryl sulfonamides in good to excellent yields under mild reaction conditions and with methanol a
- He, Yi,Li, Shi-Guang,Mbaezue, Ifenna I.,Reddy, Angula C.S.,Tsantrizos, Youla S.
-
-
- 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 0033; 0034; 0035; 0036; 0037
(2020/12/30)
-
- Electrochemical Vicinal Difluorination of Alkenes: Scalable and Amenable to Electron-Rich Substrates
-
Fluorinated alkyl groups are important motifs in bioactive compounds, positively influencing pharmacokinetics, potency and conformation. The oxidative difluorination of alkenes represents an important strategy for their preparation, yet current methods are limited in their alkene-types and tolerance of electron-rich, readily oxidized functionalities, as well as in their safety and scalability. Herein, we report a method for the difluorination of a number of unactivated alkene-types that is tolerant of electron-rich functionality, giving products that are otherwise unattainable. Key to success is the electrochemical generation of a hypervalent iodine mediator using an “ex-cell” approach, which avoids oxidative substrate decomposition. The more sustainable conditions give good to excellent yields in up to decagram scales.
- Doobary, Sayad,Sedikides, Alexi T.,Caldora, Henry P.,Poole, Darren L.,Lennox, Alastair J. J.
-
supporting information
p. 1155 - 1160
(2019/12/11)
-
- 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)
-
- Metal-free C-H Activation over Graphene Oxide toward Direct Syntheses of Structurally Different Amines and Amides in Water
-
Unprecedented metal-free synthesis of a variety of amines and amides is reported via amination of C(sp3)-H and C(sp2)-H bonds. The strategy involves graphene-oxide/I2-catalyzed nitrene insertion using PhINTs as a nitrene (NT) source in water at room temperature. A wide range of structurally different substrates, viz., cyclohexane, cyclic ethers, arenes, alkyl aromatic systems, and aldehydes/ketones, having an α-phenyl ring have been employed successfully to afford the corresponding nitrene insertion product in good yield, albeit low in few cases. The envisaged method has superiority over others in terms of its operational simplicity, metal-free catalysis, use of water as a solvent, ambient reaction conditions, and reusability of the catalyst.
- Shukla, Prashant,Asati, Ambika,Bhardiya, Smita R.,Singh, Manorama,Rai, Vijai K.,Rai, Ankita
-
p. 15552 - 15561
(2020/12/02)
-
- 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)
-
- A bifunctional strategy for N-heterocyclic carbene-stabilized iridium complex-catalyzed: N -alkylation of amines with alcohols in aqueous media
-
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)
-
- 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)
-
- Visible-light, iodine-promoted formation of n-sulfonyl imines and n-alkylsulfonamides from aldehydes and hypervalent iodine reagents
-
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
-
-
- 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)
-
- Metal-free I2O5-mediated direct construction of sulfonamides from thiols and amines
-
A simple and convenient method has been developed for the construction of sulfonamides via I2O5-mediated sulfonylation of amines with arylthiols. The present protocol provides an attractive approach to sulfonamides in moderate to good yields from readily accessible and easy to handle starting materials under mild and metal-free conditions.
- Zhu, Minghui,Wei, Wei,Yang, Daoshan,Cui, Huanhuan,Wang, Leilei,Meng, Guoqing,Wang, Hua
-
supporting information
p. 4789 - 4793
(2017/07/10)
-
- Preparation method of sulfonamides compound
-
The invention discloses a reparation method of a sulfonamides compound. The preparation method includes: using thiophenol and amine which are simple and easy to get as raw materials; enabling the raw materials to be in direct oxidation coupling reaction under mediation of safe and stable iodine pentoxide to prepare sulfonamide. The preparation method has the advantages that reaction conditions are mild (60 DEG C), the raw materials are simple and easy to get and low in price, reaction environment is friendly, a substrate is wide in application range, and metal catalysts and harsh reaction conditions like low or high temperature and zero water and zero oxygen are not needed, so that metal pollution related to common synthesis methods is avoided; the preparation method further has the advantages of simple, convenient and safe operation, stable process condition and easiness in product purification and is suitable for large-scale production.
- -
-
Paragraph 0033; 0034
(2017/09/02)
-
- Direct Sulfonamidation of Primary and Secondary Benzylic Alcohols Catalyzed by a Boronic Acid/Oxalic Acid System
-
The direct sulfonamidation of primary and secondary benzylic alcohols catalyzed by a 2,3,4,5-tetrafluorophenylboronic acid/oxalic acid co-catalytic system was examined. The reaction proceeds under mild conditions with readily available starting materials and has been shown to be gram-scalable without significant decrease of yield. Both primary and secondary benzylic alcohols were evaluated and afforded the desired sulfonamide products with good to excellent yields.
- Verdelet, Tristan,Ward, Robert M.,Hall, Dennis G.
-
p. 5729 - 5738
(2017/10/06)
-
- Metal-Free Benzylic C?H Amination via Electrochemically Generated Benzylaminosulfonium Ions
-
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)
-
- 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 0028-0031
(2016/10/10)
-
- DBN hexafluorophosphate salts as convenient sulfonylating and phosphonylating agents
-
Air-stable N-sulfonyl and N-phosphonyl DBN hexafluorophosphate salts have been synthesised under mild conditions as sulfonylating and phosphonylating agents. These salts are highly efficient in the sulfonylation and phosphonylation of a range of N- and O-nucleophiles to generate sulfonamides, sulfonate esters, phosphoramidates and phosphonate esters in good yields.
- Jones, Caroline S.,Bull, Steven D.,Williams, Jonathan M. J.
-
p. 8452 - 8456
(2016/09/28)
-
- 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)
-
- 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)
-
- Synthesis of sulfonamides via I2-mediated reaction of sodium sulfinates with amines in an aqueous medium at room temperature
-
An efficient I2-mediated approach for the synthesis of sulfonamides at room temperature using water as the solvent has been developed. This method for the synthesis of sulfonamides is quite convenient and environmentally friendly. In addition, the purification procedure of the desired products becomes very easy. This journal is
- Pan, Xiaojun,Gao, Jian,Liu, Juan,Lai, Junyi,Jiang, Huanfeng,Yuan, Gaoqing
-
supporting information
p. 1400 - 1403
(2015/03/18)
-
- 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
-
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
-
p. 447 - 459
(2014/05/20)
-
- CuI-catalyzed coupling of gem-dibromovinylanilides and sulfonamides: An efficient method for the synthesis of 2-amidoindoles and indolo[1,2-a] quinazolines
-
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
-
supporting information
p. 484 - 487
(2014/04/03)
-
- Palladium-catalyzed benzylation of arylboronic acids with N,N-ditosylbenzylamines
-
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
-
p. 4206 - 4211
(2014/05/20)
-
- 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
-
supporting information
p. 4424 - 4427
(2015/02/05)
-
- Silylium ion promoted reduction of imines with hydrosilanes
-
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
-
supporting information
p. 6643 - 6646
(2014/01/06)
-
- Direct sulfamidation of alcohols using magnetically recoverable Pd/Fe 3O4 as the catalyst
-
An efficient method is described for the direct amination of alcohols with sulfonamides using magnetically separable Pd/Fe3O4 as a catalyst without using any additives. Various alcohols such as benzylic alcohol and allylic alcohol underwent sulfamidation with sulfonamides gave the corresponding products in good to excellent yields. This effective catalyst requires no preactivation of the hydroxy group of alcohols and the reaction is environmentally benign with water as a by-product. The catalyst is completely recoverable with the simple application of an external magnetic field and the efficiency of the catalyst remains unaltered even after five cycles.
- Prasad, Aviraboina Siva,Satyanarayana, Bollikonda
-
p. 5503 - 5506,4
(2020/09/15)
-
- Half-sandwich scorpionates as nitrene transfer catalysts
-
Scorpionate complexes of the middle to late 3d transition metals [(L)M(NCMe)3](BF4)n (M = Mn, Fe, Co, Ni: 1 M, L = tris(3,5-dimethylpyrazol-1-yl)methane, TpmMe,Me, n = 2; 2M, L = tris(3-phenylpyrazol-1-yl)methane, TpmPh, n = 2; 3M except 3Mn, L = hydrotris(3,5-dimethylpyrazol-1-yl) borate, [TpMe,Me]-, n = 1; 4M, L = hydrotris(3-phenyl-5-methylpyrazol-1-yl)borate, [TpPh,Me] -, n = 1) were examined as catalysts for styrene aziridination and THF amination using phenyl-N-tosyliodinane as a nitrene donor. [(Tpm Me,Me)Fe(NCMe)3](BF4)2 (1 Fe) was identified as the most active catalyst, giving nearly quantitative nitrene transfer yields at 5 mol % loadings. The reactivity of 1Fe with a wider range of organic substrates was also explored, and a striking observation was strong selectivity for aromatic rather than benzylic amination for alkylaromatic substrates.
- Liang, Shengwen,Jensen, Michael P.
-
p. 8055 - 8058
(2013/02/22)
-
- Organic ligand-free alkylation of amines, carboxamides, sulfonamides, and ketones by using alcohols catalyzed by heterogeneous Ag/Mo oxides
-
Complicated and expensive organic ligands are normally essential in fine chemical synthesis at preparative or industrial levels. The synthesis of fine chemicals by using heterogeneous catalyst systems without additive organic ligand is highly desirable but severely limited due to their poor generality and rigorous reaction conditions. Here, we show the results of carbon-nitrogen or carbon-carbon bond formation catalyzed by an Ag/Mo hybrid material with specific Ag6Mo10O33 crystal structure. 48 nitrogen- or oxygen-containing compounds, that is, amines, carboxamides, sulfonamides, and ketones, were successfully synthesized through a borrowing-hydrogen mechanism. Up to 99% isolated yields were obtained under relatively mild conditions without additive organic ligand. The catalytic process shows promise for the efficient and economic synthesis of amine, carboxamide, sulfonamide, and ketone derivatives because of the simplicity of the system and ease of operation. Copyright
- Cui, Xinjiang,Zhang, Yan,Shi, Feng,Deng, Youquan
-
supporting information; experimental part
p. 1021 - 1028
(2011/03/20)
-
- Simple and versatile catalytic system for N-alkylation of sulfonamides with various alcohols
-
"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)
-
- Fe(II)-catalyzed N-alkylation of sulfonamides with benzylic alcohols
-
The FeCl2/K2CO3 catalyst system was developed successfully for the N-alkylation of sulfonamides with benzylic alcohols via borrowing hydrogen method. XPS analysis suggested a possible catalyst cycle between Fe(II) and Fe(0). Under the optimized condition, the scope of the protocol was demonstrated in 21 different alkylation reactions. High yields, in general >90%, are achieved in most cases.
- Cui, Xinjiang,Shi, Feng,Zhang, Yan,Deng, Youquan
-
supporting information; experimental part
p. 2048 - 2051
(2010/06/16)
-
- Copper-catalyzed N-alkylation of sulfonamides with benzylic alcohols: Catalysis and mechanistic studies
-
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
-
scheme or table
p. 2949 - 2958
(2010/03/24)
-
- Air-stable and highly active dendritic phosphine oxide-stabilized palladium nanoparticles: Preparation, characterization and applications in the carbon-carbon bond formation and hydrogenation reactions
-
Dendrimer-stabilized palladium nanoparticles were formed in the reduction of palldium bis-(acetylacetonate) [Pd(acac)2] in the presence of phosphine dendrimer ligands using hydrogen in tetrahydrofuran. The resulting Pd nanoparticles were characterized by TEM, 31P NMR and 31P MAS NMR. The results indicated that the dendritic phosphine ligandswere oxidized to phosphine oxides. These dendrimer-stabilized Pd nanoparticles were demonstrated to be efficient catalysts for Suzuki and Stille coupling reactionsand hydrogenations. The dendritic wedges served as a stabilizer for keeping the nanoparticlesfrom aggregating, and asa vehicle for facilitating the separation and/or the recycling of the Pd catalyst. In the case of the Suzuki coupling reaction, these Pd nanoparticles exhibited high catalytic efficiency (TON up to 65,000) and air stability as compared with the commonly used homogeneous catalyst tetrakis(triphenylphosphine)palladium [Pd-(PPh 3)4]. In addition, the results obtained from the bulky dendritic substrate suggest that the Pd nanoparticles might act asres ervoir of catalytically active species, and that the reaction is actually catalyzed by the soluble Pd(0) and/or Pd(II) species leached from the nanoparticle surface.
- Wu, Lei,Li, Zhi-Wei,Zhang, Feng,He, Yan-Mei,Fan, Qing-Hua
-
experimental part
p. 846 - 862
(2009/05/07)
-
- One-step synthesis of substituted dihydro- and tetrahydroisoquinolines by FeCl3·6H2O catalyzed intramolecular Friedel-Crafts reaction of benzylamino-substituted propargylic alcohols
-
(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
-
p. 1586 - 1589
(2008/09/17)
-
- Trichlorophenol (TCP) sulfonate esters: A selective alternative to pentafluorophenol (PFP) esters and sulfonyl chlorides for the preparation of sulfonamides
-
2,4,6-Trichlorophenol (TCP) sulfonate esters undergo effective aminolysis under conventional heating and microwave irradiation; the reactivity of these species is such that chemoselective transformations of PFP sulfonate esters can be achieved. The Royal Society of Chemistry.
- Wilden, Jonathan D.,Geldeard, Lynsey,Lee, Chieh C.,Judd, Duncan B.,Caddick, Stephen
-
p. 1074 - 1076
(2007/12/29)
-
- Competitive Reaction Pathways in the Nucleophilic Substitution Reactions of Aryl Benzenesulfonates with Benzylamines in Acetonitrile
-
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
-
p. 1277 - 1281
(2007/10/03)
-