- Complementary Site-Selective Sulfonylation of Aromatic Amines by Superacid Activation
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Under superacidic conditions, aniline and indole derivatives are sulfonylated at low temperature with easy-to-access arenesulfonic acids or arenesulfonyl hydrazides. By modification of the functional-group directing effect through protonation, this method allows nonclassical site functionalization by overcoming the innate regioselectivity of electrophilic aromatic substitution. This superacid-mediated sulfonylation of arenes is complementary to existing methods and can be applied, through protection by protonation, to the late-stage site-selective functionalization of natural alkaloids and active pharmaceutical ingredients.
- Bourbon, Paul,Appert, Emeline,Martin-Mingot, Agnès,Michelet, Bastien,Thibaudeau, Sébastien
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supporting information
p. 4115 - 4120
(2021/06/21)
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- Palladium-Catalyzed Direct C-H Arylation of 3-Butenoic Acid Derivatives
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We report herein a direct method to synthesize 4-aryl-3-butenoic acid through a carboxylic-acid-directed oxidative Heck reaction. The various 4-aryl-3-butenoic acids are easily prepared in moderate to good yields. In view of the promising bioactivity of 4-phenyl-3-butenoic acid previously reported, its derivatives reported here may be bioactive.
- Yang, Shan,Liu, Lingling,Zhou, Zheng,Huang, Zhibin,Zhao, Yingsheng
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supporting information
p. 296 - 299
(2021/01/13)
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- Electrochemical heterodifunctionalization of α-CF3alkenes to access α-trifluoromethyl-β-sulfonyl tertiary alcohols
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An unprecedented electrochemical heterodifunctionalization of α-CF3alkenes with benzenesulfonyl hydrazides was accomplished in this work, wherein a β-sulfonyl and a α-hydroxyl group were simultaneously incorporated across the olefinic double bond in a single operation. Consequently, a series of potentially medicinally valuable and densely functionalized α-trifluoromethyl-β-sulfonyl tertiary alcohols were assembled under mild conditions. Electrochemically-driven oxidative 1,2-difunctionlization of electron-deficient alkenes well obviates the need for oxidizing reagents, thus rendering this protocol more eco-friendly.
- Chen, Kai,Duan, Xin-Yu,Gao, Jie,Guan, Jian-Ping,Liu, Fang,Xiang, Hao-Yue,Xiao, Jun-An,Yang, Hua,Ye, Zhi-Peng
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supporting information
p. 8969 - 8972
(2021/09/10)
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- Electrochemical fluorosulfonylation of styrenes
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An environmentally friendly and efficient electrochemical fluorosulfonylation of styrenes has been developed. With the use of sulfonylhydrazides and triethylamine trihydrofluoride, a diverse array of β-fluorosulfones could be readily obtained. This reaction features mild conditions and a broad substrate scope, which could also be conveniently extended to a gram-scale preparation.
- Jiang, Yi-Min,Yu, Yi,Wu, Shao-Fen,Yan, Hong,Yuan, Yaofeng,Ye, Ke-Yin
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supporting information
p. 11481 - 11484
(2021/11/16)
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- Dual Roles of Rongalite: Reductive Coupling Reaction to Construct Thiosulfonates Using Sulfonyl Hydrazides
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A tunable and practical transformation of structurally diverse sulfonyl hydrazides into thiosulfonates in the presence of Rongalite (NaHSO 2·CH 2O) was developed. Transition-metal-free conditions, operational simplicity, and readily available reagents are the striking features of this protocol. It is the first example for the synthesis of thiosulfonates using sulfonyl hydrazides with the assistance of reductant. Additionally, the mechanistic studies revealed that this transformation probably undergoes via a reducing-coupling pathway.
- Zhang, Guofu,Fan, Qiankun,Zhao, Yiyong,Wang, Huimin,Ding, Chengrong
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supporting information
p. 81 - 85
(2020/11/03)
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- Iodine-Mediated Coupling of Cyclic Amines with Sulfonyl Hydrazides: an Efficient Synthesis of Vinyl Sulfone Derivatives
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An efficient iodine-mediated coupling of cyclic amines with sulfonyl hydrazides is reported. This transformation opens a new route to the synthesis of vinyl sulfones derivatives, which is a common structural motif in natural products and pharmaceuticals. Tentative mechanistic studies suggest that this reaction is likely to involve a radical process.
- Rong, Xiaona,Guo, Jingwen,Hu, Zheqi,Huang, Lehao,Gu, Yugui,Cai, Yuepiao,Liang, Guang,Xia, Qinqin
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supporting information
p. 701 - 708
(2020/12/30)
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- NaHSO3-Mediated Direct Synthesis of Sulfinic Esters from Sulfonyl Hydrazides under Transition-Metal-Free Conditions
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We have developed a protocol for the NaHSO3-promoted esterification of sulfonyl hydrazides with alcohols for the synthesis of sulfinic esters. Various sulfonyl hydrazides could be converted to the corresponding sulfinic esters in good to high yields. The merits of this protocol include mild transition-metal-free reaction conditions, an inexpensive and available reagent, and operational simplicity. Controlled experiments reveal that this transformation probably undergoes via a radical pathway. (Figure presented.).
- Zhang, Guofu,Fan, Qiankun,Wang, Huimin,Zhao, Yiyong,Ding, Chengrong
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supporting information
p. 833 - 837
(2020/12/07)
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- Palladium-Catalyzed Asymmetric Hydrosulfonylation of 1,3-Dienes with Sulfonyl Hydrazides
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A highly enantio- and regioselective hydrosulfonylation of 1,3-dienes with sulfonyl hydrazides has been realized by using a palladium catalyst containing a monodentate chiral spiro phosphoramidite ligand. The reaction provided an efficient approach to synthetically useful chiral allylic sulfones. Mechanistic studies suggest that the reaction proceeds through the formation of an allyl hydrazine intermediate and subsequent rearrangement to the chiral allylic sulfone product. The transformation of the allyl hydrazine intermediate to the product is the enantioselectivity-determining step.
- Li, Ming-Ming,Cheng, Lei,Xiao, Li-Jun,Xie, Jian-Hua,Zhou, Qi-Lin
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supporting information
p. 2948 - 2951
(2020/12/15)
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- Photoredox/cobaloxime co-catalyzed allylation of amines and sulfonyl hydrazines with olefins to access α-allylic amines and allylic sulfones
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Herein, we reported a dual-catalytic platform for the allylation of amines and sulfonyl hydrazines with olefins to selectively access α-allylic amines and allylic sulfones in good yields by combining photoredox catalysis and cobaloxime catalysis. This strategy avoided the use of a stoichiometric amount of terminal oxidant and the use of pre-functionalized allylic precursors, representing a green and ideal atom- & step-economical process. Good substrate scope and gram-scale synthesis demonstrated the utility of this protocol. Mechanistic studies revealed that a radical process is probably involved in this reaction.
- Tong, Qing-Xiao,Xu, Hui,Zhang, Hong,Zhong, Jian-Ji
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supporting information
p. 8227 - 8231
(2021/10/12)
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- Regio- And stereoselective electrochemical synthesis of sulfonylated enethers from alkynes and sulfonyl hydrazides
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An electrooxidative direct difunctionalization of internal alkynes with sulfonyl hydrazides has been developed for the construction of sulfonated enethers. In this transformation, metal catalysts or stoichiometric amount of oxidants are not required and molecular nitrogen and hydrogen are the sole byproducts, providing a simple and green approach for preparing various sulfonyl tetrasubstituted alkenes. Notably, the protocol could be efficiently scaled up and the follow-up procedures of the corresponding functionalized alkenes demonstrate the practicality of the electrochemical synthesis.
- Du, Wu-Bo,Wang, Ning-Ning,Pan, Chao,Ni, Shao-Fei,Wen, Li-Rong,Li, Ming,Zhang, Lin-Bao
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supporting information
p. 2420 - 2426
(2021/04/07)
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- Copper-Catalyzed Sulfonylation of Cyclobutanone Oxime Esters with Sulfonyl Hydrazides
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A copper-catalyzed radical cross-coupling of cyclobutanone oxime esters with sulfonyl hydrazides has been developed. The copper-based catalytic system proved crucial for cleavage of the C-C bond of cyclobutanone oximes and for selective C-S bond-formation involving persistent sulfonyl-metal radical intermediates. This protocol is distinguished by the low-cost catalytic system, which does not require ligand, base, or toxic cyanide salt, and by the use of readily accessible starting materials, as well as broad substrate scope, providing an efficient approach to various diversely substituted cyano-containing sulfones.
- Dong, Bingbing,Lu, Jiansha,Bao, Honghao,Zhang, Yuanyuan,Liu, Yingguo,Leng, Yuting
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supporting information
p. 3769 - 3776
(2021/07/14)
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- Small molecule-mediated induction of endoplasmic reticulum stress in cancer cells
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The endoplasmic reticulum (ER) is one of the crucial sub-cellular organelles controlling myriads of functions including protein biosynthesis, folding, misfolding and unfolding. As a result, dysregulation of these pathways in the ER is implicated in cancer development and progression. Subsequently, targeting the ER in cancer cells emerged as an interesting unorthodox strategy in next-generation anticancer therapy. However, development of small molecules to selectively target the ER for cancer therapy remained elusive and unexplored. To address this, herein, we have developed a novel small molecule library of sulfonylhydrazide-hydrazones through a short and concise chemical synthetic strategy. We identified a fluorescent small molecule that localized into the endoplasmic reticulum (ER) of HeLa cells, induced ER stress followed by triggering autophagy which was subsequently inhibited by chloroquine (autophagy inhibitor) to initiate apoptosis. This small molecule showed remarkable cancer cell killing efficacy in different cancer cells as mono and combination therapy with chloroquine, thus opening a new direction to illuminate ER-biology towards the development of novel anticancer therapeutics.
- Basu, Sudipta,Biswas, Ankur,Lahiri, Mayurika,Pandey, Shalini,Sharma, Virender Kumar
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supporting information
p. 1604 - 1611
(2021/10/23)
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- Acridine Orange Hemi(Zinc Chloride) Salt as a Lewis Acid-Photoredox Hybrid Catalyst for the Generation of α-Carbonyl Radicals
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A readily accessible organic-inorganic hybrid catalyst is reported for the reductive fragmentation of α-halocarbonyl compounds. The robust hybrid catalyst is a self-stabilizing combination of ZnCl2 Lewis acid and acridine orange as the photoactive organic dye. Mechanistic specifics of this hybrid catalyst have been studied in detail using both photophysical and electrochemical experiments. A systematic study enabled the discovery of the appropriate Lewis acid for the effective LUMO stabilization of α-halocarbonyl compounds and thereby lowering of reduction potential within the range of a standard organic dye. This strategy resolves the issues like dehalogenative hydrogenation or homo-coupling of alkyl radicals by guiding the photoredox cycle through an oxidative quenching pathway. The cooperativity between the photoactive organic dye and the Lewis acid counterparts empowers functionalization with a wide range of coupling partners through efficient and controlled generation of alkyl radicals and serves as an appropriate alternative to the expensive late transition metal-based photocatalysts. To demonstrate the application potential of this cooperative catalytic system, four different synthetic transformations of α-carbonyl bromides were explored with broad substrate scopes.
- Das, Sanju,De Sarkar, Suman,Mandal, Tanumoy
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supporting information
(2021/12/10)
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- Heterogeneous copper-catalyzed synthesis of diaryl sulfones
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A carbon-supported copper nanoparticle (Cu-NP) with high catalytic activity for the synthesis of diaryl sulfones is reported. For the first time, this Cu-NP is proved to be able to effectively promote the reaction of arylboronic acids and arylsulfonyl hydrazides to generate diaryl sulfones at room temperature. The reaction shows excellent substrate universality, and substrates with different substituents can undergo the reaction smoothly, leading to the desired products in good yields. The Cu-NP is found to be made of low valence Cu based on XRD. Hence, the reaction catalyzed by the Cu-NP is believed to involve a Cu-mediated organometallic cycle.
- Gong, Xinchi,Qu, Lingling,Shen, Zhengqi,Wang, Ganghu,Zhu, Chunyin
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supporting information
p. 10662 - 10668
(2021/12/27)
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- Synthesis of symmetrical / unsymmetrical thiosulfonates through the disproportionate coupling reaction of sulfonyl hydrazide mediated by phosphomolybdic acid
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Phosphomolybdic acid (H3PMo12O40) is reported as a green low-cost catalyst for the synthesis of symmetrical / unsymmetrical thiosulfonates via the disproportionate coupling reaction of sulfonyl hydrazide. The attributes of this reported catalytic system include low catalyst loadings (1 mol%), efficient turnover, and high yields (up to 94%). Additionally, this reaction mechanism involves the formation of a thiyl radical and sulfonyl radical via sulfinyl radical disproportionation.
- Lv, Mengting,Liu, Yufeng,Li, Ke,Yang, Guoping
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supporting information
(2021/01/21)
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- Electrochemical Annulation-Iodosulfonylation of 1,5-Enyne-containing para-Quinone Methides (p-QMs) to Access (E)-Spiroindenes
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A new electrochemical three-component annulation-iodosulfonylation of 1,5-enyne-containing para-quinone methides (p-QMs) has been established by using available arylsulfonyl hydrazides and potassium iodide under environmentally benign conditions. The electrosynthesis offers sustainable and efficient access to construct spirocyclohexadienone-containing (E)-indenes without any additional catalyst or oxidant through a sulfonyl-radical-triggered 1,6-addition and an I+-mediated ipso-cyclization cascade. Notably, potassium iodide plays the triple role of an electrolyte, a redox catalyst, as well as an iodination reagent.
- Zuo, Hang-Dong,Zuo, Hang-Dong,Hao, Wen-Juan,Zhu, Chi-Fan,Zhu, Chi-Fan,Guo, Cheng,Tu, Shu-Jiang,Jiang, Bo
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supporting information
p. 4471 - 4477
(2020/06/04)
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- TBAB-catalyzed 1,6-conjugate sulfonylation of paraquinone methides: A highly efficient approach to unsymmetrical gem-diarylmethyl sulfones in water ?
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A highly efficient sulfonylation of para-quinone methides with sulfonyl hydrazines in water has been developed on the basis of the mode involving a tetrabutyl ammonium bromide (TBAB)-promoted sulfa-1,6-conjugated addition pathway. This reaction provides a green and sustainable method to synthesize various unsymmetrical diarylmethyl sulfones, showing good functional group tolerance, scalability, and regioselectivity. Further transformation of the resulting diarylmethyl sulfones provides an efficient route to some functionalized molecules.
- Liu, Zhang-Qin,You, Peng-Sheng,Zhang, Liang-Dong,Liu, Da-Qing,Liu, Sheng-Shu,Guan, Xiao-Yu
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supporting information
(2020/02/11)
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- Electrochemically Induced Synthesis of Sulfonylated N-Unsubstituted Enamines from Vinyl Azides and Sulfonyl Hydrazides
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Sulfonylated N-unsubstituted enamines were synthesized through a chain of chemical and electrochemical transformations via sulfonylation of vinyl azides. The disclosing of the N-unsubstituted enamines synthesis was based on a unique property of the azido group, which is its ability to eliminate the N2 molecule. Furthermore, a formal paradox is observed: A double bond reacts and a double bond is retained. Electrosynthesis proceeded in an undivided cell equipped with a graphite anode and a stainless steel cathode; NH4I was used as a supporting electrolyte.
- Mulina, Olga M.,Zhironkina, Nataliya V.,Paveliev, Stanislav A.,Demchuk, Dmitry V.,Terent'Ev, Alexander O.
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supporting information
p. 1818 - 1824
(2020/03/04)
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- Designing heterocyclic chalcones, benzoyl/sulfonyl hydrazones: An insight into their biological activities and molecular docking study
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The aim of this study is to investigate the antioxidant, anticholinesterase and the antiproliferative activities of some chalcones, benzoyl and sulfonyl hydrazones. The antioxidant activity was studied by way of four complimentary assays and the anticholinesterase activity was studied using the Ellman method. The antiproliferative activity of the compounds was determined using a BrdU cell proliferation ELISA assay. Compound 32 (IC50: 15.58 ± 0.01 μg/mL) against the brain (C6) and 29 (IC50: 5.02 ± 0.05 μg/mL) against cervical (HeLa) cancer cell lines exhibited higher antiproliferative activity than the other compounds. Two sulfonyl hydrazone derivatives 45 and 47 exhibited very good antioxidant activity. The results of anticholinesterase activity indicated that nine compounds 3, 8, 10, 14, 24, 25, 27, 38, and 45 significantly inhibited acetylcholinesterase enzymes and thirty-three compounds 1–4, 7–14, 22–28, 32–41, 44–47 inhibited butyrylcholinesterase enzymes (BChE) more than galantamine. In addition, virtual screening methods based on ligand 45 having the best activity against BChE was used to define new human BChE inhibitors. The interactions of ligand 8 against acetylcholinesterase (AChE) were also examined. Important key residues were determined and visualized on completion of the methodology. All calculations indicated the suitability of use of the molecular docking approach for understanding interaction mechanisms and crucial fragments of novel hit compounds such as the potential lead AChE and BChE inhibitor candidates.
- ?ztürk, Mehmet,Demirta?, Ibrahim,Iyido?an, Ay?egül Karakü?ük,Kur?un Aktar, Bedriye Seda,Oru?-Emre, Emine El?in,S?cak, Yusuf,Tok, Tu?ba Ta?k?n,Ya?l?o?lu, Ayse ?ahin
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- The synthesis of sulfonated 4: H -3,1-benzoxazines via an electro-chemical radical cascade cyclization
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A new route for the synthesis of sulfonated 4H-3,1-benzoxazines has been accomplished by electrochemical radical cascade cyclizations of styrenyl amides with sulfonylhydrazines. This process demonstrates a wide substrate scope with diverse functional group compatibility under metal- and external oxidant-free conditions at ambient temperature.
- He, Tian-Jun,Huang, Jing-Mei,Zhong, Wei-Qiang
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supporting information
p. 2735 - 2738
(2020/03/17)
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- CuCl2-promoted decomposition of sulfonyl hydrazides for the synthesis of thiosulfonates
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Sulfonyl hydrazides recently received much attention as reagents for the introduction of sulfur-containing functional groups into organic compounds, because both sulfonyl and sulfenyl sources could be generated by the oxidation and decomposition of the sulfonyl hydrazides, respectively. However, the transformations of sulfonyl hydrazides into thiosulfonates, which could be produced by the reaction between sulfonyl and sulfenyl sources, have been less investigated. In this manuscript, we describe CuCl2-promoted selective synthesis of thiosulfonates from sulfonyl hydrazides. A variety of thiosulfonates were produced in moderate to good yields. The mechanism involving radical intermediates such as sulfonyl radical and thiyl radical was proposed on the basis of the previously reported references and mechanistic investigations. In addition, quantum chemical simulations revealed that Cu-promoted decomposition of sulfonyl hydrazides is thermodynamically viable in the developed conditions.
- Kim, Junsu,Park, Sanggil,Kim, Hyungjun,Kim, Jinho
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supporting information
(2020/07/02)
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- An Alternative Metal-Free Aerobic Oxidative Cross-Dehydrogenative Coupling of Sulfonyl Hydrazides with Secondary Phosphine Oxides
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An alternative metal-free, efficient and practical approach for the preparation of phosphinothioates is established via the aerobic oxidative cross-dehydrogenative coupling (CDC) of sulfonyl hydrazides with secondary phosphine oxides catalyzed by tetrabutylammonium iodide (TBAI) in the presence of atmospheric oxygen. The strategy provides an array of diverse phosphinothioates in good to excellent yields. Furthermore, two representative bioactive molecules are synthesized on up to gram scale by utilizing this method.
- Cheng, Feixiang,Liu, Jianjun,Liu, Teng,Yu, Rong,Zhang, Yanqiong
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p. 253 - 262
(2019/12/28)
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- Metal-Free Electrochemical Coupling of Vinyl Azides: Synthesis of Phenanthridines and β-Ketosulfones
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We reported an efficient and environmentally benign electrochemical synthesis of phenanthridines by oxidative coupling of vinyl azides with sodium azide or benzenesulfonyl hydrazides, for the first time. The reaction conditions are mild, and no additional metal-catalyst or exogenous oxidants are needed. The protocol has broad substrate scope and high functional group tolerance. Furthermore, this green electrochemical procedure can be readily extended to the synthesis of β-ketosulfones. Gram scale reactions further demonstrate the practicability.
- Chen, Qianjin,Kong, Xianqiang,Li, Guodong,Liang, Qi,Lin, Long,Xu, Bo,Yu, Ke
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supporting information
p. 6135 - 6145
(2020/10/06)
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- One-pot synthesis of β-ketosulfones from sulfonyl chloride, hydrazine hydrate and vinyl azide in water
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A novel, facile and efficient strategy for the one-pot synthesis of β-ketosulfones from readily available sulfonyl chloride, hydrazine hydrate and vinyl azides is described. The reaction proceeded very smoothly affording diverse β-ketosulfones in moderate to good yields. This new procedure has the advantages of environmental benign, easy and simple operation, low cost and wide tolerance of functional groups, which provides a highly fascinating protocol to access β-ketosulfones.
- Zhang, Yaohong,Luo, Mengqiang,Li, Yan,Shen, Runfu,Qi, Chenze,Wang, Hai,Cheng, Kai
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supporting information
(2020/10/26)
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- Electrochemical Coupling of Arylsulfonyl Hydrazides and Tertiary Amines for the Synthesis of β-Amidovinyl Sulfones
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The reaction of arylsulfonyl hydrazides with tertiary amines provided β-amidovinyl sulfones in good yields under mild electrochemical conditions. The reactions were carried out using an acid, in a solution of nBu4NBF4 in dimethyl sulfoxide in undivided cells with graphite-platinum electrodes under a constant current. The arylsulfonyl hydrazides and tertiary amines were activated via a radical process by electrochemical oxidation and reacted to give the desired β-amidovinyl sulfones.
- Kim, Han-Sung,Lee, Sunwoo
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supporting information
p. 6951 - 6955
(2019/11/13)
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- TBN-mediated regio- and stereoselective sulfonylation & oximation (oximosulfonylation) of alkynes with sulfonyl hydrazines in EtOH/H2O
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An alkyne difunctionalization cascade reaction was developed to generate α-sulfonylethanone oximes under metal-free conditions. The reaction features environmentally benign EtOH/H2O as a solvent, a broad substrate scope and easily scaled up for gram-scale synthesis. The reaction mechanism was illustrated with UPLC, GC-MS and UPLC-tof/MS.
- Wang, Bin,Yan, Zicong,Liu, Liyan,Wang, Jiawei,Zha, Zhenggen,Wang, Zhiyong
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supporting information
p. 205 - 212
(2019/01/28)
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- Synergy of anodic oxidation and cathodic reduction leads to electrochemical deoxygenative C2 arylation of quinoline: N-oxides
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The first example of electrochemical deoxygenative C2 arylation of quinoline N-oxides using sulfonyl hydrazines was demonstrated in this work. By employing both anodic oxidation and cathodic reduction, a variety of 2-arylquinolines were synthesized under metal catalyst-, exogenous-oxidant-, and exogenous-reductant-free conditions.
- Yuan, Yong,Jiang, Minbao,Wang, Tao,Xiong, Yunkui,Li, Jun,Guo, Huijiao,Lei, Aiwen
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supporting information
p. 11091 - 11094
(2019/09/20)
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- Palladium-Catalyzed Regio- and Stereoselective Sulfonylation of Aryl Propiolates with Sulfonyl Hydrazides: Access to (E)-β-Aryl Sulfonyl Acrylates
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An efficient method for the synthesis of (E)-β-aryl sulfonyl acrylates has been reported. This palladium-catalyzed approach showed excellent regio- and stereoselectivity in the sulfonylation of aryl propiolates with sulfonyl hydrazides. Through this approach, a wide range of (E)-β-aryl sulfonyl acrylates were obtained in moderate to high yields. (Figure presented.).
- Jiang, Huanfeng,Yan, Wuxin,Huang, Jiuzhong,Tan, Chaowei,Zhan, Lingzhi,Wu, Wanqing
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supporting information
p. 4575 - 4580
(2019/09/16)
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- Arylsulfonylhydrazone induced apoptosis in MDA-MB-231 breast cancer cells
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Background: Breast cancer is the most frequent cancer among women. Chemotherapy is necessary for treating metastatic disease and represents an important therapeutic approach, although antineoplastic drugs have high toxicity and may be limited by the development of drug resistance. These problems impose an urgent need to discover new anticancer agents and, so, arylsulfonylhydrazone analogues were designed, synthesized, and evaluated with regard to their cytotoxic activity against breast cancer cells in order to identify novel potential antitumor agents. Methods: Synthesis was performed as previously described by Fernandes and co-workers. Cytotoxicity of sulfonylhydrazones against MDA-MB-231, MCF-7 and 3T3 cells was evaluated by MTT method. Apoptotic effects was verified by Annexin-V/PI assay, Hoechst stain and propidium iodide stain. Molecular modeling was executed using Spartan’10 version 1.1.0. Geometry optimization was performed by the MMFF, PM6 and Hartree-Fock 3-31G* methods and electronic and lipophilic properties were computed. Results: Thirteen analogues were synthesized, which 3f and 4f were cytotoxic against evaluated breast cancer cells. The most promising compound, 3f, showed IC50 values equal to 104.6 and 142.4 μM for MDA-MB-231 and MCF-7, respectively. 3f induced apoptosis, causing phosphatidylserine externalization, pyknosis, and cell cycle arrest in the G0/G1 phase in MDA-MB-231 breast cancer cells. Furthermore, 3f was selective for tumor cells when compared to 3T3 fibroblasts. Structure-activity relationship suggests that introduction of a benzodioxol group increased cytotoxicity and superior lipophilicity may be related to superior activity. Conclusion: Sulfonylhydrazone analogues presented good activity against breast cancer cells by inducing apoptosis and might be a promising scaffold to further molecular modifications persuing more effective antitumoral agents.
- Fernandes, Thais Batista,de Azevedo, Ricardo Alexandre,Yang, Rosania,Teixeira, Sarah Fernandes,Trossini, Gustavo Henrique Goulart,Barbuto, José Alexandre Marzag?o,Ferreira, Adilson Kleber,Parise-Filho, Roberto
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p. 1288 - 1298
(2018/11/01)
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- Copper-mediated sulfonylation of aryl iodides and bromides with arylsulfonyl hydrazides in PEG-400
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Sulfonylation using stable and readily available arylsulfonyl hydrazides and aryl iodides or bromides mediated by cupric acetate has been achieved. Using polyethylene glycol (PEG-400) as an eco-friendly medium, the coupling reaction could afford a series of unsymmetrical diaryl sulfones in moderate to good yields without the presence of additional ligands and base.
- Wu, Xiangmei,Wang, Yan
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supporting information
p. 10953 - 10957
(2018/07/06)
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- Palladium-Catalyzed Regio- and Stereoselective Coupling-Addition of Propiolates with Arylsulfonyl Hydrazides: A Pattern for Difunctionalization of Alkynes
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A new pattern for difunctionalization of alkynes via a palladium-catalyzed regio- and stereoselective coupling-addition of propiolates with arylsulfonyl hydrazides is disclosed. The approach enables the synthesis of various highly functionalized (E)-vinylsulfones in satisfactory yields. Arylsulfonyl hydrazides act as both aryl and sulfonyl sources via selective cleavage of Ar(C)-S and S-N bonds, which are simultaneously incorporated onto the terminal carbon atom of an alkyne molecule.
- Liu, Lixin,Sun, Kang,Su, Lebin,Dong, Jianyu,Cheng, Lei,Zhu, Xiaodong,Au, Chak-Tong,Zhou, Yongbo,Yin, Shuang-Feng
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supporting information
p. 4023 - 4027
(2018/07/15)
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- Exogenous-oxidant-free electrochemical oxidative C-H sulfonylation of arenes/heteroarenes with hydrogen evolution
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An efficient and environmentally benign electrochemical oxidative radical C-H sulfonylation of arenes/heteroarenes was developed in this work. A series of significant diarylsulfones were prepared under mild catalyst- and exogenous-oxidant-free reaction conditions, which efficiently avoid the issues of desulfonylation or over-reduction of sulfonyl groups.
- Yuan, Yong,Yu, Yi,Qiao, Jin,Liu, Pan,Yu, Banying,Zhang, Wukun,Liu, Huilin,He, Min,Huang, Zhiliang,Lei, Aiwen
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supporting information
p. 11471 - 11474
(2018/10/20)
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- Copper-Catalyzed Radical Cascade Cyclization to Access 3-Sulfonated Indenones with the AIE Phenomenon
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An efficient copper-catalyzed radical cascade cyclization strategy was developed, by which a wide variety of 3-sulfonyl substituted indenones were prepared in one pot via reaction of 2-alkynylbenzonitriles with sulfonyl hydrazides in the presence of TBHP and CuI under mild reaction conditions. Much more importantly, the 3-sulfonyl indenones, synthesized through our newly developed copper-catalyzed radical cascade cyclization strategy, were found to own typical aggregation-induced emission (AIE) properties, showing orange to red emission with large Stokes shift (more than 135 nm). In addition, such newly found AIEgens could be successfully used in live cell imaging, exhibiting excellent biocompatibility and application potential.
- Sun, Kai,Chen, Xiao-Lan,Li, Shi-Jun,Wei, Dong-Hui,Liu, Xiao-Ceng,Zhang, Yin-Li,Liu, Yan,Fan, Lu-Lu,Qu, Ling-Bo,Yu, Bing,Li, Kai,Sun, Yuan-Qiang,Zhao, Yu-Fen
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p. 14419 - 14430
(2018/11/23)
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- Copper-catalyzed: S -methylation of sulfonyl hydrazides with TBHP for the synthesis of methyl sulfones in water
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A copper-catalyzed S-methylation of sulfonyl hydrazides with TBHP was efficiently developed, providing a variety of methyl sulfones with good to excellent yields. The reaction can be carried out in water smoothly without any ligand or additive under mild conditions and this catalyst-in-water can be recycled several times.
- Yang, Yu,Bao, Yajie,Guan, Qianqian,Sun, Qi,Zha, Zhenggen,Wang, Zhiyong
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supporting information
p. 112 - 116
(2017/08/15)
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- Base-mediated tandem sulfonylation and oximation of alkenes in water
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A base-mediated bifunctionalization of alkenes for the synthesis of α-sulfonylethanone oximes was developed in water under metal-free conditions. This reaction features a wide substrate scope and facile starting materials to afford the desired products in high yields.
- Wang, Bin,Tang, Lin,Liu, Liyan,Li, Yanan,Yang, Yu,Wang, Zhiyong
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supporting information
p. 5794 - 5799
(2017/12/26)
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- Gold-Catalyzed Dehydrazinative C(sp)–S Coupling Reactions of Arylsulfonyl Hydrazides with Ethynylbenziodoxolones for Accessing Alkynyl Sulfones
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A gold(III)-catalyzed dehydrazinative coupling reaction between arylsulfonyl hydrazides and ethynylbenziodoxolone reagents was realized for the synthesis of alkynyl sulfones. The scope and versatility of the reaction were demonstrated by the efficient synthesis of 23 derivatives with diverse structural features.
- Shinde, Popat S.,Patil, Nitin T.
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p. 3512 - 3515
(2017/07/04)
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- Palladium-Catalyzed Desulfitative Cross-Coupling of Arylsulfonyl Hydrazides with Terminal Alkynes: A General Approach toward Functionalized Internal Alkynes
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A palladium-catalyzed Sonogashira-type coupling between arylsulfonyl hydrazides and terminal alkynes via Ar(C)-S bond cleavage is disclosed, which enables the general synthesis of functionalized internal alkynes, especially the Br-substituted ones, in good to excellent yields under acid- and base-free conditions.
- Qian, Liang-Wei,Sun, Mengli,Dong, Jianyu,Xu, Qing,Zhou, Yongbo,Yin, Shuang-Feng
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p. 6764 - 6769
(2017/07/15)
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- Catalyst-free synthesis of 3-sulfone nitrile from sulfonyl hydrazides and acrylonitrile in water
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A novel catalyst-free sulfonation reaction for synthesizing 3-sulfone nitrile compounds from sulfonyl hydrazides and acrylonitriles in water, without any metal catalyst, ligand or organic solvent, was demonstrated. This catalyst-free protocol provides a new synthetic method for the construction of 3-sulfone nitrile compounds with excellent yields. The D2O experiment adequately proved that the catalyst-free sulfonation reaction occurs via a Michael addition mechanism and that the hydrogen of 3-sulfone nitrile comes from water.
- Li, Wei,Gao, Lingfeng,Zhuge, Wenyun,Sun, Xu,Zheng, Gengxiu
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supporting information
p. 7819 - 7823
(2017/10/06)
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- Catalyst-free thiolation of indoles with sulfonyl hydrazides for the synthesis of 3-sulfenylindoles in water
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A catalyst-free thiolation of indoles with sulfonyl hydrazides was efficiently developed in water under mild conditions without any ligand or additive. The reaction provided a variety of 3-sulfenylindoles with good to excellent yields and the only by-products were nitrogen and water.
- Yang, Yu,Zhang, Sheng,Tang, Lin,Hu, Yanbin,Zha, Zhenggen,Wang, Zhiyong
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supporting information
p. 2609 - 2613
(2016/05/24)
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- Oxysulfonylation of Alkenes with Sulfonyl Hydrazides under Transition-Metal-Free Conditions
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A novel method to synthesise β-keto sulfones is demonstrated by Br?nsted acid promoted oxysulfonylation of alkenes with sulfonyl hydrazides under transition-metal-free conditions. The reaction selectively affords structurally diverse β-keto sulfones in good to excellent yields in a 9:1 mixture of acetonitrile/water.
- Liu, Congrong,Ding, Lianghui,Guo, Guang,Liu, Weiwei
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supporting information
p. 910 - 912
(2016/03/01)
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- Palladium-catalyzed direct arylation of indoles with arylsulfonyl hydrazides
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A novel method to synthesise 2-arylindoles is demonstrated via direct arylation of indoles with arylsulfonyl hydrazides. Under the optimized reaction conditions, the reaction well tolerates a wide variety of functional groups to afford structurally diverse 2-arylindoles in good to excellent yields at 70 °C.
- Liu, Congrong,Ding, Lianghui,Guo, Guang,Liu, Weiwei,Yang, Fu-Lai
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supporting information
p. 2824 - 2827
(2016/03/12)
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- Copper-Catalyzed Aerobic Oxidative Reaction of Sulfonyl Hydrazides with Alcohols: An Easy Access to Sulfinates
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A Cu-catalyzed aerobic oxidative reaction between sulfonyl hydrazides and alcohols has been developed. In this reaction, sulfonyl hydrazides act as the sulfinic acid precursors to react with alcohols, resulting in sulfinic esters with up to 72 % yield. This catalytic system tolerates a wide range of sulfonyl hydrazide substrates, and represents a new strategy for the transformation of readily available sulfonyl hydrazides.
- Du, Bingnan,Li, Zan,Qian, Ping,Han, Jianlin,Pan, Yi
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supporting information
p. 478 - 481
(2016/03/08)
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- Synthesis and potential anticonvulsant activity of new aryl sulfonyl semicarbazide derivatives
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In the present study on the development of new anticonvulsants, twelve new aryl sulfonyl semicarbazide derivatives were synthesized and tested for anticonvulsant activity using maximal electroshock (MES), subcutaneous pentylenetetrazole screens. Their neurotoxicity was determined by the rotorod test. The most active compound 5i showed the MES-induced seizures with ED50 value of 7.3?mg/kg and TD50 value of 402.3?mg/kg after intraperitoneally injection to mice, which provided compound 5i with a protective index (TD50/ED50) of 55.1 in the MES test.
- Nie, Yousong,Zhong, Min,Jiang, Zhiyuan,Sun, Jian,Gao, Yangguang,Ding, Fei,Li, Hang,Zhang, Yongmin,He, Xianran
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p. 1425 - 1432
(2016/07/06)
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- Microwave-assisted synthesis of new sulfonyl hydrazones, screening of biological activities and investigation of structure–activity relationship
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Abstract: Sulfonyl hydrazone scaffold and the piperidine rings have important role in medicinal chemistry. This study shows the synthesis of two novel series of sulfonyl hydrazone having piperidine derivatives by condensing benzene sulfonyl hydrazides with ethyl 4-oxopiperidine-1-carboxylate and 2,6-diphenylpiperidin-4-one. Physical and chemical properties of compounds have been characterized and reported by utilizing their melting point, elemental analysis, IR, 1H-NMR, 13C NMR, 2D NMR and mass spectra results. Synthesized compounds were evaluated for antioxidant capacity and anticholinesterase activity. The antioxidant capacity of the compounds were screened through four complementary test, i.e., β-carotene–linoleic acid for lipid peroxidation, DPPH free radical (DPPH·), ABTS cation radical (ABTS+·) and CUPRAC assays. Assay results showed that N′-(2,6-diphenylpiperidin-4-ylidene)-4-bromobenzenesulfonohydrazide (11) has the highest lipid peroxidation inhibitory activity. Within the assay series, N′-(2,6-diphenylpiperidin-4-ylidene)-4-bromobenzenesulfonohydrazide (11) exhibited better activity than standard BHT in DPPH· scavenging, while N′-(2,6-diphenylpiperidin-4-ylidene)benzenesulfonohydrazide (10) showed the best ABTS+· scavenging assay. The CUPRAC assay revealed that ethyl 4-(2-(4-methoxyphenylsulfonyl)hydrazono)piperidine-1-carboxylate (5) indicated the best activity with A0.50 value among the tested compounds than the antioxidant standard α-tocopherol. According to AChE assay, N′-(2,6-diphenylpiperidin-4-ylidene)-4-chlorobenzenesulfonohydrazide (12) had the best activity, while in BChE assay the highest activity was found for compound N′-(2,6-diphenylpiperidin-4-ylidene)-4-methylbenzenesulfonohydrazide (16). Electronic and structural characteristics and density functional studies of the all newly synthesized compounds have been reported for better understanding in molecular-level. NMR, molecular electrostatic potential (MEP), ΔEHOMO–LUMO band gap and the dipole moments of the molecules have been also analyzed and reported. Graphical Abstract: [Figure not available: see fulltext.]
- Karaman, Nurcan,Oru?-Emre, Emine El?in,S?cak, Yusuf,?at?kka?, Berna,Karakü?ük-?yido?an, Ay?egül,?ztürk, Mehmet
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p. 1590 - 1607
(2016/07/30)
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- Palladium-catalyzed allylation of sulfonyl hydrazides with alkynes to synthesize allylic arylsulfones
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A novel method for the construction of allyl arylsulfone derivatives was developed by palladium catalyzed allylation of sulfonyl hydrazides with alkynes. A series of structurally diverse allyl arylsulfones can be regioselectively synthesized in high yields under mild conditions.
- Lu, Chuan-Jun,Chen, Hong,Chen, Dong-Kai,Wang, Hong,Yang, Zhen-Ping,Gao, Jianrong,Jin, Hongwei
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p. 10833 - 10839
(2016/12/06)
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- P-Toluenesulphonic acid-promoted, I2-catalysed sulphenylation of pyrazolones with aryl sulphonyl hydrazides
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Aryl pyrazolone thioethers were synthesized via the I2-catalysed cross-coupling of pyrazolones with aryl sulphonyl hydrazides in the presence of p-toluenesulphonic acid, which has been proposed to promote the reaction by facilitating the decomposition of sulphonyl hydrazides. This journal is
- Zhao, Xia,Zhang, Lipeng,Li, Tianjiao,Liu, Guiyan,Wang, Haomeng,Lu, Kui
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supporting information
p. 13121 - 13123
(2014/12/11)
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- Catalyst-free sulfonylation of activated alkenes for highly efficient synthesis of mono-substituted ethyl sulfones in water
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A catalyst-free sulfonylation reaction of activated alkenes with sulfonyl hydrazides was efficiently developed under mild and environmentally benign conditions, in water without any ligand or additive. The reaction gave a range of structurally diverse mono-substituted ethyl sulfones with excellent yields, in which the by-product was nitrogen. the Partner Organisations 2014.
- Yang, Yu,Tang, Lin,Zhang, Sheng,Guo, Xuefeng,Zha, Zhenggen,Wang, Zhiyong
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supporting information
p. 4106 - 4109
(2014/10/15)
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- Palladium-catalyzed conjugate addition of arylsulfonyl hydrazides to α,β-unsaturated ketones
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A palladium-catalyzed desulfitative-denitrogenative conjugate addition of arylsulfonyl hydrazides to α,β-unsaturated ketones is described. The reaction showed very good selectivity and tolerated a wide range of functionalities under an atmosphere of oxygen with or without the aid of a metal co-oxidant. The Royal Society of Chemistry 2013.
- Chen, Wen,Chen, Hui,Xiao, Fuhong,Deng, Guo-Jun
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supporting information
p. 4295 - 4298
(2013/08/23)
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- Discovery of novel 2-piperidinol-3-(arylsulfonyl)quinoxalines as phosphoinositide 3-kinase α (PI3Kα) inhibitors
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A series of novel 2-aliphatic cyclic amine-3-(arylsulfonyl)quinoxalines was synthesized based on the structural features of a previously identified lead, WR1. The 2-piperidinol-3-(arylsulfonyl)quinoxalines, which showed excellent antitumor activities against five human cell lines, with inhibitory activities ranging from 0.34 to 2.32 μM, proved to be a promising class of novel PI3Kα inhibitors. The most potent compound 10d (WR23) showed an inhibitory IC50 value of 0.025 μM against PI3Kα and significant pAkt suppression effect. Molecular docking analysis was performed to determine possible binding modes between PI3Kα and target compounds.
- Wu, Peng,Su, Yi,Liu, Xiaowen,Yang, Bo,He, Qiaojun,Hu, Yongzhou
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scheme or table
p. 2837 - 2844
(2012/07/01)
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- Oxidative Mizoroki-Heck-type reaction of arylsulfonyl hydrazides for a highly regio- and stereoselective synthesis of polysubstituted alkenes
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A useful source: Arylsulfonyl hydrazides have been identified as synthetically useful aryl sources for the Pd(OAc)2 catalyzed oxidative Mizoroki-Heck-type reaction under molecular oxygen to provide a convenient access to polysubstituted alkenes in a highly regio- and stereoselective manner (see scheme). The reaction well tolerates various functional groups such as alkoxy, halo, alcohol, carboxylic acid, ester, amide, sulfonamide, and sulfone. Copyright
- Yang, Fu-Lai,Ma, Xian-Tao,Tian, Shi-Kai
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supporting information; experimental part
p. 1582 - 1585
(2012/03/11)
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