- Diastereoselective synthesis of conformationally restricted KOR agonists
-
In order to analyze the bioactive conformation of flexible KOR agonists the ethylenediamine KOR pharmacophore was conformationally constrained by incorporation into a bicyclic system. For this purpose, 2-azabicyclo[3.2.1.]octan-7-amines were designed, synthesized and pharmacologically evaluated. The primary amine 14 as first key intermediate was prepared in a six-step synthesis starting with methyl cyclopent-3-enecarboxylate 9. Whereas phenylacetamides failed to provide bicyclic compounds, the intramolecular nucleophilic substitution of the sulfonamide 25 was initiated by deprotonation with NaH affording the bicyclic compound 26 in 72% yield. The three-step introduction of the pharmacophoric pyrrolidine ring started with nucleophilic substitution of exo-configured tosylate 26 with NaN3, which unexpectedly occurred under retention of configuration leading to exo-configured azide 31. The final KOR agonists 35 and 36 with exo-configured amino moieties were obtained by removal of the N-tosyl moiety of 33 and introduction of the second pharmacophoric element by acylation with dihalophenylacetyl chlorides. The KOR affinity of the pyrrolidine 35a is in the high nanomolar range (Ki = 862 nM). The low KOR affinity is explained by a non-appropriate dihedral angle of 137°/141° of the N(pyrrolidine)-C-C-N(acyl) system. As observed for stereoisomers of potent KOR agonists, phenylacetamide 35a and more importantly sulfonamides 33a and 33b show moderate affinity at σ1 receptors (Ki = 109-208 nM). This journal is
- Ilari, Denise,Maskri, Sarah,Schepmann, Dirk,K?hler, Jens,Daniliuc, Constantin G.,Koch, Oliver,Wünsch, Bernhard
-
p. 4082 - 4099
(2021/05/19)
-
- Synthesis method of aryl tertiary sulfonamide compounds promoted by visible light
-
The invention provides a synthesis method of aryl tertiary sulfonamide compounds promoted by visible light. In a non-protonic solvent, N-benzyl tertiary amine and arylsulfonyl chloride are used as rawmaterials, under the conditions of photosensitizer catalysis and illumination, a reaction is carried out for 1-4h at room temperature, and then separation and purification are carried out to obtain the product. The synthesis method of the aryl tertiary sulfonamide compound provided by the invention has the advantages of mild reaction conditions, simplicity and convenience in operation, short reaction time, no need of any transition metal catalysis and environmental friendliness.
- -
-
Paragraph 0021-0022
(2021/01/25)
-
- Facile synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazides
-
A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazide with NXS (X = Cl or Br) and late-stage conversion to several other functional groups was described. A variety of nucleophiles could be engaged in this transformation, thus permitting the synthesis of complex sulfonamides and sulfonates. In most cases, these reactions are highly selective, simple, and clean, affording products at excellent yields.
- Chen, Rongxiang,Xu, Shaohong,Shen, Fumin,Xu, Canran,Wang, Kaikai,Wang, Zhanyong,Liu, Lantao
-
-
- Method for preparing N-sulfonyl tetrahydropyrrole compound by using gold complex
-
The invention relates to a method for preparing an N-sulfonyl tetrahydropyrrole compound by using a gold complex, which comprises the following step of: reacting a sulfonamide compound and a tetrahydrofuran compound as raw materials with a gold complex containing an ortho-carborane Schiff base ligand as a catalyst at room temperature to obtain the N-sulfonyl tetrahydropyrrole compound. Compared with the prior art, the method has the advantages that the gold complex containing the ortho-carborane Schiff base ligand is adopted as the catalyst, the sulfonamide compound and the tetrahydrofuran compound can be catalyzed to react under the room temperature condition to prepare the N-sulfonyl tetrahydropyrrole compound, the usage amount of the catalyst is low, the reaction condition is mild, the reaction rate is high, the product yield is high, the substrate is high in universality, the raw materials are cheap and easy to obtain, and the method has a wide application prospect in industry.
- -
-
Paragraph 0054-0059
(2021/07/17)
-
- Water soluble homogeneous catalysts that are recoverable by phase selectivity and host-guest interactions
-
A chemical reaction is catalyzed in an organic solvent using a water soluble N-heterocyclic carbene homogeneous catalyst to form a reaction mixture. An aqueous phase in the reaction mixture. A solvent in which the catalyst is insoluble is added to the reaction mixture, causing the catalyst to migrate to the aqueous phase to form a catalyst-laden aqueous phase. The catalyst is extracted from the catalyst-laden aqueous phase.
- -
-
Page/Page column 2
(2020/08/30)
-
- Synthesis method of beta-aryl sulfonyl enamine compound
-
The invention belongs to the technical field of organic synthesis. The invention relates to the technical field of organic synthesis, in particular to a synthesis method of a beta-aryl sulfonyl enamine compound, which comprises the following steps: in an air environment, with a sodium benzenesulfinate derivative and tertiary amine as substrates, carrying out anodic oxidation coupling reaction in amixture of an electrolyte and a solvent to obtain the beta-aryl sulfonyl enamine compound. The synthesis method of the beta-aryl sulfonyl enamine compound provided by the invention is free of metal,oxidant and halogen, the whole synthesis process is harmless to the environment, and a variety of beta-aryl sulfonyl enamine compounds with satisfactory yield can be obtained.
- -
-
Paragraph 0036-0039
(2020/05/29)
-
- 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)
-
- NEW SELECTIVE MODULATORS OF INSECT NICOTINIC ACETYLCHOLINE RECEPTORS
-
The present invention relates to a compound having the following formula (I): wherein: - A is a (hetero)aryl radical comprising from 5 to 10 carbon atoms, possibly substituted by at least one substituent chosen from the group consisting of: halogen atoms, amino, azido, cyano, nitro, hydroxyl, formyl, carboxyl, amido, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, alkenyl groups, cycloalkenyl groups, and alkynyl groups, and - R is H, CN or CF3, or their pharmaceutically acceptable salts, racemates, diastereomers or enantiomers.
- -
-
Page/Page column 19; 22
(2020/06/01)
-
- Iodine-catalyzed sulfonylation of sulfonyl hydrazides with: Tert -amines: A green and efficient protocol for the synthesis of sulfonamides
-
This study provides a direct, sustainable and eco-friendly method for the synthesis of various sulfonamides via the sulfonylation of sulfonyl hydrazides with tert-amines. The method utilizes sulfonyl hydrazides to oxidize and couple with tertiary amines through selective cleavage of C-N bonds. In this reaction, molecular iodine was used as the catalyst and t-butyl hydroperoxide was used as the oxidant.
- Chen, Jinyang,Han, Xiaoran,Mei, Lan,Liu, Jinchuan,Du, Kui,Cao, Tuanwu,Li, Qiang
-
p. 31212 - 31216
(2019/10/19)
-
- 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)
-
- TBAI-catalyzed selective synthesis of sulfonamides and β-aryl sulfonyl enamines: coupling of arenesulfonyl chlorides and sodium sulfinates with tert-amines
-
A simple, practical and metal-free method has been developed for the synthesis of sulfonamides and β-arylsulfonyl enamines via the selective cleavage of C-N and C-H bonds through the iodine-catalyzed oxidation of arenesulfonyl chlorides and sodium sulfinates with tert-amines. The method uses commercially available inexpensive catalysts and oxidants, and has a wide substrate scope and operational simplicity.
- Jiang, Hongmei,Tang, Xiaoyue,Xu, Zhihui,Wang, Huixian,Han, Kang,Yang, Xiaolan,Zhou, Yuanyuan,Feng, Yong-Lai,Yu, Xian-Yong,Gui, Qingwen
-
p. 2715 - 2720
(2019/03/12)
-
- Charge-Transfer Complex Promoted Regiospecific C?N Bond Cleavage of Vicinal Tertiary Diamines
-
A catalyst-free, charge-transfer complex promoted coupling of sulfonyl chlorides with vicinal tertiary diamines to generate sulfonamides is presented. Mechanistic studies showed that these reactions are proceeded via charge transfer of vicinal tertiary diamines to sulfonyl chlorides, forming the unstable sulfonyl quaternary ammonium like complexes which induced the regiospecific intramolecular C?N bond cleavage of vicinal tertiary diamines. (Figure presented.).
- Fu, Ying,Xu, Qin-Shan,Shi, Chun-Zhao,Du, Zhengyin,Xiao, Caiqin
-
supporting information
p. 3502 - 3506
(2018/09/14)
-
- Systematic Evaluation of 2-Arylazocarboxylates and 2-Arylazocarboxamides as Mitsunobu Reagents
-
2-Arylazocarboxylate and 2-arylazocarboxamide derivatives can serve as replacements of typical Mitsunobu reagents such as diethyl azodicarboxylate. A systematic investigation of the reactivity and physical properties of those azo compounds has revealed that they have an excellent ability as Mitsunobu reagents. These reagents show similar or superior reactivity as compared to the known azo reagents and are applicable to the broad scope of substrates. pKa and steric effects of substrates have been investigated, and the limitation of the Mitsunobu reaction can be overcome by choosing suitable reagents from the library of 2-arylazocarboxylate and 2-aryl azocarboxamide derivatives. Convenient recovery of azo reagents is available by one-pot iron-catalyzed aerobic oxidation, for example. SC-DSC analysis of representative 2-arylazocarboxylate and 2-arylazocarboxamide derivatives has shown high thermal stability, indicating that these azo reagents possess lower chemical hazard compared with typical azo reagents.
- Hirose, Daisuke,Gazvoda, Martin,Ko?mrlj, Janez,Taniguchi, Tsuyoshi
-
p. 4712 - 4729
(2018/04/26)
-
- Synthesis of aromatic sulfonamides through a copper-catalyzed coupling of aryldiazonium tetrafluoroborates, DABCO·(SO2)2, and N-Chloroamines
-
A copper-catalyzed aminosulfonylation of aryldiazonium tetrafluoroborates, DABCO·(SO2)2, and N-chloroamines is described. This coupling reaction provides an efficient and simple approach to a wide range of sulfonamides in moderate to good yields under mild conditions. Mechanistic investigation suggests that a radical process and transition-metal catalysis are merged in this tandem reaction.
- Zhang, Feng,Zheng, Danqing,Lai, Lifang,Cheng, Jiang,Sun, Jiangtao,Wu, Jie
-
supporting information
p. 1167 - 1170
(2018/02/23)
-
- Method for synthesizing benzenesulfonamide compound by using benzenesulfonohydrazide derivative and secondary amine through metal-free catalysis
-
The invention provides a method for synthesizing a benzenesulfonamide compound by using a benzenesulfonohydrazide derivative and secondary amine through metal-free catalysis. The method comprises thefollowing steps: taking the benzenesulfonohydrazide deri
- -
-
Paragraph 0022-0024
(2019/01/08)
-
- 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)
-
- Method for synthesizing benzenesulfonamide compound by using benzenesulfonyl chloride compound and secondary amine through metal-free catalysis
-
The invention provides a method for synthesizing a benzenesulfonamide compound by using a benzenesulfonyl chloride compound and secondary amine through metal-free catalysis. The method comprises the following steps: taking the benzenesulfonamide compound
- -
-
Paragraph 0022; 0023; 0024
(2019/01/08)
-
- 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 0031; 0032
(2017/09/02)
-
- I2/TBHP Mediated C-N and C-H Bond Cleavage of Tertiary Amines toward Selective Synthesis of Sulfonamides and β-Arylsulfonyl Enamines: The Solvent Effect on Reaction
-
A novel method toward synthesis of sulfonamides and β-arylsulfonyl enamines has been developed via I2/TBHP mediated C-N and C-H bond cleavage of tertiary amines, which features highly selective formation of two different target products depending on the reaction solvent. The experimental results reveal that H2O as the solvent could effectively achieve the C-N bond cleavage to produce sulfonamides due to H2O participating in the reaction process where H2O plays a dual role. Differing from H2O, organic solvents (such as dimethyl sulfoxide) could promote the C-H bond cleavage of tertiary amines to yield β-arylsulfonyl enamines.
- Lai, Junyi,Chang, Liming,Yuan, Gaoqing
-
supporting information
p. 3194 - 3197
(2016/07/14)
-
- Metal-free synthesis of sulfonamides via iodine-catalyzed oxidative coupling of sulfonyl hydrazides and amines
-
A novel, rapid, and environmentally-friendly protocol for the synthesis of sulfonamides using iodine as catalyst under solvent-free conditions is described. This method involves the oxidative coupling of sulfonyl hydrazides and amines in the presence of catalytic amount of iodine using TBHP as oxidant. This protocol does not require purification techniques such as column chromatography and recrystalization.
- Parumala, Santosh Kumar Reddy,Peddinti, Rama Krishna
-
supporting information
p. 1232 - 1235
(2016/03/01)
-
- Electrochemical synthesis of sulfonamides from arenesulfonohydrazides or sodium p-methylbenzenesulfinate and amines
-
An efficient electrochemical synthesis of sulfonamides (yields 56–98%) from arenesulfonohydrazides or sodium p-methylbenzenesulfinate and amines was performed in an undivided cell with graphite anode and iron cathode in MeCN–H2O medium using halides as redox mediators and supporting electrolytes.
- Terent'ev, Alexander O.,Mulina, Olga M.,Pirgach, Dmitry A.,Syroeshkin, Mikhail A.,Glinushkin, Alexey P.,Nikishin, Gennady I.
-
p. 538 - 539
(2016/12/02)
-
- NH4I-Catalyzed Synthesis of Sulfonamides from Arylsufonylhydrazides and Amines
-
A novel and efficient approach to sulfonamides has been developed. Using TBHP as the oxidant and NH4I (20 mol%) as the catalyst, arylsulfonyl hydrazides reacted with amines to provide sulfonamides in moderate to good yields. Possible reaction pathway for the formation of the products was also discussed in this paper. Sulfonimides were synthesized through the oxidation coupling of arylsufonylhydrazides and amines by TBHP/NH4I system in moderate to good yields.
- Yu, Hui,Zhang, Yonghao
-
supporting information
p. 359 - 362
(2016/04/26)
-
- Advances and mechanistic insight on the catalytic Mitsunobu reaction using recyclable azo reagents
-
Ethyl 2-arylhydrazinecarboxylates can work as organocatalysts for Mitsunobu reactions because they provide ethyl 2-arylazocarboxylates through aerobic oxidation with a catalytic amount of iron phthalocyanine. First, ethyl 2-(3,4-dichlorophenyl)hydrazinecarboxylate has been identified as a potent catalyst, and the reactivity of the catalytic Mitsunobu reaction was improved through strict optimization of the reaction conditions. Investigation of the catalytic properties of ethyl 2-arylhydrazinecarboxylates and the corresponding azo forms led us to the discovery of a new catalyst, ethyl 2-(4-cyanophenyl)hydrazinecarboxylates, which expanded the scope of substrates. The mechanistic study of the Mitsunobu reaction with these new reagents strongly suggested the formation of betaine intermediates as in typical Mitsunobu reactions. The use of atmospheric oxygen as a sacrificial oxidative agent along with the iron catalyst is convenient and safe from the viewpoint of green chemistry. In addition, thermal analysis of the developed Mitsunobu reagents supports sufficient thermal stability compared with typical azo reagents such as diethyl azodicarboxylate (DEAD). The catalytic system realizes a substantial improvement of the Mitsunobu reaction and will be applicable to practical synthesis.
- Hirose, Daisuke,Gazvoda, Martin,Ko?mrlj, Janez,Taniguchi, Tsuyoshi
-
p. 5148 - 5159
(2016/07/29)
-
- Electrochemical Oxidative Amination of Sodium Sulfinates: Synthesis of Sulfonamides Mediated by NH4I as a Redox Catalyst
-
An efficient protocol for the synthesis of sulfonamides via the electrochemical oxidative amination of sodium sulfinates has been developed. The chemistry proceeds in a simple undivided cell employing a substoichiometric amount of NH4I that serves both as a redox catalyst and a supporting electrolyte; in this manner additional conducting salt is not required. A wide range of substrates, including aliphatic or aromatic secondary and primary amines, as well as aqueous ammonia, proved to be compatible with the protocol. Scale-up was possible, thereby demonstrating the practicality of the approach. The electrolytic process avoids the utilization of external oxidants or corrosive molecular iodine and therefore represents an environmentally benign means by which to achieve the transformation.
- Jiang, Yang-Ye,Wang, Qing-Qing,Liang, Sen,Hu, Li-Ming,Little, R. Daniel,Zeng, Cheng-Chu
-
p. 4713 - 4719
(2016/07/06)
-
- Iodine-catalyzed expeditious synthesis of sulfonamides from sulfonyl hydrazides and amines
-
A new synthesis of sulfonamides has been developed via an iodine-catalyzed sulfonylation of amines with arylsulfonyl hydrazides. This metal-free strategy employs readily accessible and easy to handle starting materials, catalysts and oxidants, and can be easily conducted under mild conditions, providing a convenient access to a wide range of sulfonamides in moderate to excellent yields within a short reaction time.
- Yotphan, Sirilata,Sumunnee, Ladawan,Beukeaw, Danupat,Buathongjan, Chonchanok,Reutrakul, Vichai
-
p. 590 - 597
(2016/01/12)
-
- A One-Pot, fast, and efficient amidation of carboxylic acids, α-amino acids and sulfonic acids using pph3/n-chlorobenzotriazole system
-
Triphenylphosphine (PPh3)/N-chlorobenzotriazole (NCBT), and amine (primary and secondary aliphatic amines and also substituted anilines) in CH2Cl2 efficiently converted carboxylic acids, α-amino acids, and sulfonic acids to the corresponding amides and sulfonamides at room temperature. Good to excellent yields, inexpensive, and fast reaction conditions are the important features of this procedure.
- Rouhi-Saadabad, Hamed,Akhlaghinia, Batool
-
p. 1703 - 1714
(2015/09/15)
-
- N-alkylation of sulfonamides with alcohols by Tf2O
-
N-sulfonylpyrrolidines and N-alkyl sulfonamides were efficiently prepared via alkylation of sulfonamides with 1,4- diols or alcohols by Tf2O. The reaction occurred under mild reaction conditions in moderate to high yields and tolerated aryl and aliphatic sulfonamides.
- Yu, Ting Ting,Qi, Lan-Jun,Cui, Dong-Mei,Zhang, Chen,Zhao, Yan
-
supporting information
p. 610 - 612
(2015/08/04)
-
- Chemoselective Intramolecular Functionalization of Methyl Groups in Nonconstrained Molecules Promoted by N-Iodosulfonamides
-
Mechanistic evidence observed in Hofmann-L?ffler-Freytag-type reactions has been crucial to achieve the chemoselective functionalization of methyl groups under mild conditions. Radical-mediated methyl iodination and subsequent oxidative deiodination are the key steps in this functionalization, where iodine chemistry has a pivotal role on the formation of the C-N bond. The concepts of single hydrogen atom transfer (SHAT) and multiple hydrogen atom transfer (MHAT) are introduced to describe the observed chemoselectivity. (Chemical Equation Presented).
- Paz, Nieves R.,Rodríguez-Sosa, Dionisio,Valdés, Haydee,Marticorena, Ricardo,Melián, Daniel,Copano, M. Belén,González, Concepción C.,Herrera, Antonio J.
-
p. 2370 - 2373
(2015/06/02)
-
- Visible-light-promoted remote C(sp3)-H amidation and chlorination
-
A visible-light-promoted C(sp3)-H amidation and chlorination of N-chlorosulfonamides (NCSs) is reported. This remote C(sp3)-H functionalization can be achieved in weak basic solution at room temperature with as little as 0.1 mol % of
- Qin, Qixue,Yu, Shouyun
-
supporting information
p. 1894 - 1897
(2015/04/27)
-
- 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)
-
- Iodine-catalyzed oxidative amination of sodium sulfinates: A convenient approach to the synthesis of sulfonamides under mild conditions
-
The iodine-catalyzed oxidative amination of sodium sulfinates in the presence of sodium percarbonate as the oxidant has been developed. The reaction shows good substrate scope and tolerates a wide range of functionalities in both amine and sodium sulfinate substrates. Aliphatic amines, heteroaromatic amines and hydrochloride salts of amines canbe employed as the amine sources in this transformation. Mechanistic studies indicated that a radical pathway might be involved in the reaction process. This transition-metalfree protocol offers an alternative and convenient approach for a preparation of a series of sulfonamides in moderate to good yields under mild conditions.
- Buathongjan, Chonchanok,Beukeaw, Danupat,Yotphan, Sirilata
-
p. 1575 - 1582
(2015/03/04)
-
- Tandem ring-closing metathesis/transfer hydrogenation: Practical chemoselective hydrogenation of alkenes
-
An operationally simple chemoselective transfer hydrogenation of alkenes using ruthenium metathesis catalysts is presented. Of great practicality, the transfer hydrogenation reagents can be added directly to a metathesis reaction and effect hydrogenation of the product alkene in a single pot at ambient temperature without the need to seal the vessel to prevent hydrogen gas escape. The reduction is applicable to a range of alkenes and can be performed in the presence of aryl halides and benzyl groups, a notable weakness of Pd-catalyzed hydrogenations. Scope and mechanistic considerations are presented.
- Connolly, Timothy,Wang, Zhongyu,Walker, Michael A.,McDonald, Ivar M.,Peese, Kevin M.
-
p. 4444 - 4447
(2015/01/09)
-
- Stability and activity of cis-dichloro ruthenium olefin metathesis precatalysts bearing chelating sulfur alkylidenes
-
S-Chelated Grubbs type complexes are usually found in their stable cis-dichloro conformation. These precatalysts are usually latent and necessitate external stimuli to promote olefin metathesis reactions. Herein we report the synthesis of new S-chelated ruthenium complexes, by a simple exchange of the benzylidene to an alkylidene chelating ligand. The structure of the complexes was studied by NMR spectroscopy, single crystal X-ray diffraction and DFT calculations. The new complexes were tested in a series of olefin metathesis reactions and were found to be the first cis-dichloro ruthenium precatalysts that are active at room temperature. The observed differences in reactivity and structure between the alkylidene complexes and their benzylidene counterparts highlight the important influence aromaticity may have on the stability and activity of chelated Grubbs type complexes. The findings may also have implications to develop alternative strategies to stabilize, or destabilize, other organometallic complexes bearing relevant chelating ligands.
- Tzur, Eyal,Ivry, Elisa,Diesendruck, Charles E.,Vidavsky, Yuval,Goldberg, Israel,Lemcoff, N. Gabriel
-
supporting information
p. 24 - 28
(2014/08/18)
-
- Br?nsted acid-assisted N-alkylation of sulfonamides using ethers as the alkylation reagents
-
N-Alkylation of sulfonamides using cyclic ethers as alkylation reagents and Br?nsted acid as a catalyst produced pyrrolidine and piperidine derivatives in good yields. When using symmetrical and unsymmetrical ethers as alkylation reagents, mono-N-alkylation of sulfonamides took place to afford the corresponding products.
- Shi, Wei,Bai, Chun-Mei,Zhu, Kai,Cui, Dong-Mei,Zhang, Chen
-
p. 434 - 438
(2014/01/06)
-
- Breaking the dichotomy of reactivity vs. chemoselectivity in catalytic SN1 reactions of alcohols
-
The inability to decouple Lewis acid catalysis from undesirable Bronsted acid catalysed side reactions when water or other protic functional groups are necessarily present has forced chemists to choose between powerful but harsh catalysts or poor but mild
- Hellal, Malik,Falk, Florian C.,Wolf, Elena,Dryzhakov, Marian,Moran, Joseph
-
supporting information
p. 5990 - 5994
(2014/08/05)
-
- Metal-free oxidative coupling of amines with sodium sulfinates: A mild access to sulfonamides
-
A practical and mild procedure for the preparation of sulfonamides through TBAI-catalyzed oxidative coupling of amines with sodium sulfinates using TBHP as an oxidant was presented. A variety of amines and sodium sulfinates could go through the transformation, without impacting the hydroxyl group. This journal is
- Zhao, Jinwu,Xu, Jingxiu,Chen, Jiaxi,Wang, Xiaoqin,He, Minghua
-
p. 64698 - 64701
(2015/04/27)
-
- Imidazolium-salt-functionalized ionic-CNT-supported Ru-carbene/palladium nanoparticles for recyclable tandem metathesis/hydrogenation reactions in ionic liquids
-
NP and tuck: Two different catalysts, a Ru-carbene complex and palladium nanoparticles, were immobilized onto the same imidazolium-salt-functionalized ionic CNTs. These supported dual-function catalysts showed excellent catalytic activity in tandem metathesis/hydrogenation reactions in an ionic liquid and could be recovered and reused four times. RCM=ring-closing metathesis. Copyright
- Lee, Sujin,Shin, Ju Yeon,Lee, Sang-Gi
-
supporting information
p. 1990 - 1993
(2013/09/23)
-
- Indium triiodide catalyzed reductive functionalization of amides via the single-stage treatment of hydrosilanes and organosilicon nucleophiles
-
The indium triiodide catalyzed single-stage cascade reaction of N-sulfonyl amides with hydrosilanes and two types of organosilicon nucleophiles such as silyl cyanide and silyl enolates selectively promoted deoxygenative functionalization to give α-cyanoamines and β-aminocarbonyl compounds, respectively.
- Inamoto, Yoshihiro,Kaga, Yuta,Nishimoto, Yoshihiro,Yasuda, Makoto,Baba, Akio
-
supporting information
p. 3452 - 3455
(2013/07/26)
-
- Copper-catalyzed sulfonamides formation from sodium sulfinates and amines
-
A new and convenient method for the construction of sulfonamides via a copper-catalyzed oxidative coupling between sodium sulfinates and amines with 1 atm O2 or DMSO as the oxidant was described. This method provides efficient and robust synthesis of functional sulfonamides in good yields and excellent chemoselectivity. And detailed mechanistic studies showed that this transformation may go through a single electron transfer (SET) pathway.
- Tang, Xiaodong,Huang, Liangbin,Qi, Chaorong,Wu, Xia,Wu, Wanqing,Jiang, Huanfeng
-
supporting information
p. 6102 - 6104
(2013/07/11)
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- Synthesis and characterization of new ruthenium N-heterocyclic carbene Hoveyda II-type complexes. Study of reactivity in ring closing metathesis reactions
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This manuscript describes the synthesis and structural study of new second generation Hoveyda-Grubbs catalysts: 1,3-dimesityl-acenaphthylenyl-4,5- imidazolin-2-ylidene (BIAN-NHC) ruthenium isopropoxybenzylidene dichloride 3 and 1,3-bis(2,6-dimethylphenyl)
- Merino, Estibaliz,Poli, Evelyne,Diaz, Urbano,Brunel, Daniel
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supporting information
p. 10913 - 10918
(2012/10/29)
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- NAlkylation of tosylamides using esters as primary and tertiary alkyl sources: Mediated by hydrosilanes activated by a ruthenium catalyst
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Select your group: Either a primary or tertiary alkyl group can be selectively introduced onto the nitrogen atom of tosylamides in a ruthenium-catalyzed reaction employing hydrosilanes through a judicious choice in the esters that serve as the alkyl source (see scheme; Ts= 4-toluenesulfonyl). These N-alkylation reactions are useful for construction of naturally occurring azacyclic skeletons. Copyright
- Nishikata, Takashi,Nagashima, Hideo
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supporting information; experimental part
p. 5363 - 5366
(2012/07/03)
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- DABCO-bis (sulfur dioxide), DABSO, as a convenient source of sulfur dioxide for organic synthesis: Utility in sulfonamide and sulfamide preparation
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The charge-transfer complex generated from the combination of DABCO and sulfur dioxide, DABSO, is a bench-stable colorless solid suitable for use in organic synthesis as a replacement for gaseous sulfur dioxide. The complex can be combined with Grignard reagents to form sulfinates, which can then be converted in situ to a series of sulfonamides. Alternatively, reaction with anilines and iodine leads to the formation of a series of sulfamides. Cheletropic addition between DABSO and 2,3-dimethylbutadiene provides the corresponding sulfolene.
- Woolven, Holly,Gonzalez-Rodriguez, Carlos,Marco, Isabel,Thompson, Amber L.,Willis, Michael C.
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p. 4876 - 4878
(2011/12/05)
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- One-pot synthesis of sulfonamides from methyl sulfinates using ultrasound
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Room temperature ultrasonic irradiation of neat mixtures of methyl sulfinates and primary or secondary amines (1.5 equiv) produced sulfinamides, which on m-CPBA oxidation (in dichloromethane) were converted into the corresponding sulfonamides. The two steps can be accomplished in one pot, in good overall yields, when using secondary amines, but primary amines give better sulfonamide yields when the peracid oxidation is effected on the purified sulfinamide. This constitutes a mild, efficient, and potentially scalable route to sulfonamides, which obviates the use of water sensitive, often lachrymatory sulfonyl chlorides and large reagent excesses.
- García Ruano, José L.,Parra, Alejandro,Marzo, Leyre,Yuste, Francisco,Mastranzo, Virginia M.
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experimental part
p. 2905 - 2910
(2011/05/05)
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- Aryl(sulfonyl)amino group: A convenient and stable yet activated modification of amino group for its intramolecular displacement
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Aryl(sulfonyl)amino groups, readily derived from sulfonyl- or arylamines by standard methods as well as the recently introduced methods of sulfonylation and arylation, proved to be good leaving groups in intramolecular substitution reactions by various nitrogen, oxygen, and carbon nucleophiles.
- Kato, Yuzo,Yen, Dinh Hoang,Fukudome, Yasuhiro,Hata, Takeshi,Urabe, Hirokazu
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supporting information; scheme or table
p. 4137 - 4139
(2010/11/04)
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- One-Pot synthesis of sulfonamides from primary and secondary amine derived sulfonate salts using cyanuric chloride
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A convenient, mild and efficient one-pot synthesis of new sulfonamides is described. The reaction of primary or secondary amine derived sulfonate salts in the presence of cyanuric chloride, triethylamine as base, and anhydrous acetonitrile as solvent at room temperature gives the corresponding sulfonamides in good to excellent yields. Georg Thieme Verlag Stuttgart.
- Rad, Mohammad Navid Soltani,Khalafi-Nezhad, Ali,Asrari, Zeinab,Behrouz, Somayeh,Amini, Zohreh,Behrouz, Marzieh
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experimental part
p. 3983 - 3988
(2010/03/26)
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- Gold-catalyzed substitution reaction with ortho-alkynylbenzoic acid alkyl ester as an efficient alkylating agent
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ortho-Alkynylbenzoic acid alkyl esters behave as alkylating agents in combination with gold catalysts. The reaction with alcohols occurs smoothly in the presence of catalytic amounts of Ph3PAuCl and AgOTf under mild conditions to produce the corresponding ether products in high yields. The protocol is also useful for Friedel-Crafts alkylation and N-alkylation of sulfonamides. The reaction likely proceeds through the gold-induced in situ construction of leaving groups and subsequent nucleophilic attack of nucleophiles, such as alcohols, aromatic compounds, and sulfonamides.
- Aikawa, Haruo,Tago, Sakie,Umetsu, Kazuteru,Haginiwa, Naomichi,Asao, Naoki
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experimental part
p. 1774 - 1784
(2009/06/20)
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- Synthesis of 8-hydroxyquinolines with amino and thioalkyl functionalities at position 4
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(Chemical Equation Presented) Six 8-hydroxyquinolines with amino and thioalkyl functionalities at position 4 have been prepared. The synthesis starts with chlorination of the readily available 4-hydroxy-8-tosyloxyquinoline to give 4-chloro-8-tosyloxyquinoline in 94% yield. Treatment of the 4-chloro-8-tosyloxyquinoline with sulphur and nitrogen nucleophiles produces the target 4-amino and 4-thioalkyl-8-hydroxyquinolines in more than 70% yield. In case of sulphur nucleophiles and pyrrolidine, the removal of the protecting tosyl group at position 8 occurs simultaneously with the substitution of chlorine at position 4.
- Omar, Walaa A. E.,Heiskanen, Juha P.,Hormi, Osmo E. O.
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p. 593 - 595
(2008/09/19)
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- Expedient synthesis of sulfinamides from sulfonyl chlorides
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Sulfinamides were synthesized from sulfonyl chlorides using a procedure involving in situ reduction of sulfonyl chlorides. The reaction is broad in scope and easy to perform.
- Harmata, Michael,Zheng, Pinguan,Huang, Chaofeng,Gomes, Maria G.,Ying, Weijiang,Ranyanil, Kanok-On,Balan, Gayatri,Calkins, Nathan L.
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p. 683 - 685
(2007/10/03)
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