- Iron Hydride Radical Reductive Alkylation of Unactivated Alkenes
-
Iron-catalyzed hydrogen atom transfer-mediated intermolecular C-C coupling reactions between alkenes and tosylhydrazones, followed by in situ cleavage of the tosylhydrazine intermediates using Et3N, are described. The process involves a new strategic bond disconnection resulting in the reductive alkylation of nonactivated alkenes. The reaction is operationally simple, proceeds under mild conditions, and has a wide substrate scope.
- Saladrigas, Mar,Bonjoch, Josep,Bradshaw, Ben
-
-
Read Online
- N-tosylhydrazones as acceptors for nucleophilic alkyl radicals in photoredox catalysis: A short case study on possible side reactions
-
We report the attempted development of a photoredox-catalyzed α-C–H alkylation reaction of aliphatic amine derivatives, using N-tosylhydrazones as radical alkylating partners. The original intention was to intercept α-aminoalkyl radical intermediates with
- Cresswell, Alexander J.,Kinsella, Anna G.,Stead, Darren,Tibbetts, Joshua D.
-
supporting information
(2022/01/31)
-
- Pd-Catalyzed Cascade Metallo-Ene Cyclization/Metallo-Carbene Coupling of Allenamides
-
A highly efficient palladium-catalyzed cascade metallo-ene/metallo-carbene coupling reaction was developed to produce 2,3-dihydropyrrole derivatives in high yields. In this transformation, two new Csp3?Csp2 and Csp2?Cspsu
- Cao, Chengqiang,Yang, Yi,Li, Xin,Liu, Yunxia,Liu, Hui,Zhao, Zengdian,Chen, Lei
-
supporting information
p. 1538 - 1542
(2021/03/01)
-
- Mn(III)-mediated phosphinoylation of aldehyde hydrazones: Direct “one-pot” synthesis of α-iminophosphine oxides from aldehydes
-
A “one-pot” strategy for the straightforward Mn(III)-mediated phosphinoylation of aldehyde hydrazones with diphenylphosphine oxide to furnish α-iminophosphine oxides is described. This mild and practical method allows the direct use of aldehydes as substrates in one pot to generate the hydrazones, which are then engaged “in situ” by the phosphorus reagent in the presence of Mn(OAc)3 oxidant. Thus, the requisite isolation of the hydrazones is not needed in this operation. Conducted mechanistic experiments implicate a pathway involving phosphorus-centered radicals.
- Bian, Xue-Wei,Zhang, Ling,Shoberu, Adedamola,Zou, Jian-Ping
-
supporting information
(2021/04/02)
-
- Selective hydrolysis of phosphorus(v) compounds to form organophosphorus monoacids
-
An azide and transition metal-free method for the synthesis of elusive phosphonic, phosphinic, and phosphoric monoacids has been developed. Inert pentavalent P(v)-compounds (phosphonate, phosphinate, and phosphate) are activated by triflate anhydride (Tf2O)/pyridine system to form a highly reactive phosphoryl pyridinium intermediate that undergoes nucleophilic substitution with H2O to selectively deprotect one alkoxy group and form organophosphorus monoacids.
- Ash, Jeffrey,Cordero, Paula,Huang, Hai,Kang, Jun Yong
-
p. 6007 - 6014
(2021/07/21)
-
- Visible-Light-Catalyzed in Situ Denitrogenative Sulfonylation of Sulfonylhydrazones
-
A photocatalyzed in situ denitrogenative sulfonylation of N-arylsulfonyl hydrazones has been developed. This transformation provides a low-carbon strategy to assemble arylalkyl sulfones in a stepwise denitrogenation/sulfonylation manner.
- Huang, Xiang,Chen, Xing,Xie, Haisheng,Tan, Zheng,Jiang, Huanfeng,Zeng, Wei
-
supporting information
p. 6784 - 6788
(2021/09/08)
-
- Palladium-Catalyzed Three-Component Coupling Reaction of o-Bromobenzaldehyde, N-Tosylhydrazone, and Methanol
-
A ligand-controlled palladium-catalyzed three-component reaction of o-bromobenzaldehyde, N-tosylhydrazone, and methanol is described. This reaction uses readily available compounds as starting materials while displaying a broad substrate scope and good functional group compatibility.
- Zhu, Lei,Ren, Xiaojian,Yu, Yinghua,Ou, Pengcheng,Wang, Zhi-Xiang,Huang, Xueliang
-
supporting information
p. 2087 - 2092
(2020/03/04)
-
- Divergent Synthesis of Vinyl-, Benzyl-, and Borylsilanes: Aryl to Alkyl 1,5-Palladium Migration/Coupling Sequences
-
Organosilicon compounds have been extensively utilized both in industry and academia. Studies on the syntheses of diverse organosilanes is highly appealing. Through-space metal/hydrogen shifts allow functionalization of C?H bonds at a remote site, which are otherwise difficult to achieve. However, until now, an aryl to alkyl 1,5-palladium migration process seems to have not been presented. Reported herein is the remote olefination, arylation, and borylation of a methyl group on silicon to access diverse vinyl-, benzyl-, and borylsilanes, constituting a unique C(sp3)?H transformation based on a 1,5-palladium migration process.
- Han, Jie-Lian,Ju, Cheng-Wei,Qin, Ying,Zhao, Dongbing
-
supporting information
p. 6555 - 6560
(2020/03/03)
-
- Photoisomerization-enhanced 1,3-dipolar cycloaddition of carbon-bridged octocyclic azobenzene with photo-released nitrile imine for peptide stapling and imaging in live cells
-
A photo-induced 1,3-dipolar cycloaddition between nitrile imine and highly ring-strained NN double bond as a dipolarophile was discovered. The photo-isomerization of carbon-bridged octocyclic azobenzene (CBOA) into its trans-configuration accelerates the ligation reaction at a very rapid rate (28 400 M-1 s-1). The CBOA-based photo-click reaction was proved to be bioorthogonal. In addition, the NoxaB peptide was successfully cross-linked by a CBOA stapler which plays a dual role: Photo-control of the conformation of the peptide and photo-conjugation of probes in live cells.
- Deng, Jiajie,Guo, Guiling,Wu, Xueting,Yu, Zhipeng,Zhao, Xiaohu
-
supporting information
p. 5602 - 5607
(2020/08/21)
-
- Copper-catalyzed cross-coupling and sequential allene-mediated cyclization for the synthesis of 1,2,3-triazolo[1,5-a]quinolines
-
In this paper, a tandem reaction involving copper-catalyzed cross-coupling and allene-mediated cyclization of 1-(2-ethynylaryl)-1,4-disubstituted-1,2,3-triazole withN-tosylhydrazone has been developed. This method features operational simplicity, excellen
- Jiang, Yubo,Ren, Yongsheng,Xiao, Tiebo,Xiong, Shaoqi,Yang, Jianhua
-
supporting information
p. 7174 - 7182
(2020/10/02)
-
- One-Pot Reaction between N-Tosylhydrazones and 2-Nitrobenzyl Bromide: Route to NH-Free C2-Arylindoles
-
A one-pot Barluenga coupling between N-tosylhydrazones and nitro-benzyl bromide, followed by deoxygenation of ortho-nitrostyrenes, and subsequent cyclization has been developed, providing a new way to synthesize various C2-arylindoles. This method exhibits a good substrate scope and functional group tolerance, and it allows an access to NH-free indoles, which can present a potential utility in medicinal chemistry applications.
- Bzeih, Tourin,Zhang, Kena,Khalaf, Ali,Hachem, Ali,Alami, Mouad,Hamze, Abdallah
-
p. 228 - 238
(2019/01/04)
-
- Rhodium(III)-Catalyzed Directed C-H Dienylation of Anilides with Allenes Leads to Highly Conjugated Systems
-
Allenes are unique coupling partners in transition-metal-catalyzed C-H functionalization leading to a variety of products via alkenylation, allenylation, allylation, and annulation reactions. The outcome is governed by both the reactivity of the allene and the formation and stability of the organometallic intermediate. An efficient Rh(III)-catalyzed, weakly coordinating group-directed dienylation of electronically unbiased allenes is developed using an N-acyl amino acid as a ligand. Further elaboration of the dienylated products to construct polycyclic compounds is also described.
- Ghosh, Chiranjit,Nagtilak, Prajyot Jayadev,Kapur, Manmohan
-
supporting information
(2019/05/08)
-
- Substituent-Oriented Synthesis of Substituted Pyrazoles/Chromeno[3,2- c]pyrazoles via Sequential Reactions of Chromones/3-Chlorochromones and Tosylhydrazones
-
A facile and efficient synthetic strategy for the chemoselective synthesis of monocyclic/tricyclic-fused pyrazoles was developed, and it was oriented by different 3-position substituents (H or Cl) on the chromones. The reaction proceeded in a one-pot sequential way with a broad substrate scope and moderate to excellent yields.
- Dai, Tianzi,Li, Qunyi,Zhang, Xiaofei,Yang, Chunhao
-
p. 5913 - 5921
(2019/05/10)
-
- Selective C?C Coupling of Vinyl Epoxides with Diborylmethide Lithium Salts
-
Vinyl epoxides and styrene oxide can react with diborylmethide lithium salts through an exclusive SN2 borylmethylation/ring opening in a regio- and diastereoselective way, depending on the nature of the substrate. The ring-opening protocol prov
- Gava, Riccardo,Fernández, Elena
-
supporting information
p. 8013 - 8017
(2019/05/29)
-
- Copper-catalyzed one-pot coupling reactions of aldehydes (ketones), tosylhydrazide and 2-amino(benzo)thiazoles: An efficient strategy for the synthesis of N-alkylated (benzo)thiazoles
-
An efficient and practical C–N bond formation methodology for the synthesis of N-alkylated (benzo)thiazoles was developed, via the copper-catalyzed one-pot two-step reactions of 2-amino(benzo)thiazoles and aldehydes (ketones) with tosylhydrazide. This cross-coupling reaction proceeded smoothly and tolerated a broad range of functional groups (46 examples). A variety of functionalized N-alkylated (benzo)thiazoles were obtained in moderate to high yields. Notably, gram-scale synthesis of fanetizole (anti-inflammatory drug) was also realized through this protocol.
- Xie, Zengyang,Chen, Ruijiao,Ma, Mingfang,Kong, Lingdong,Liu, Jun,Wang, Cunde
-
-
- Palladium-catalyzed cascade reactions of alkene-tethered carbamoyl chlorides with: N-tosyl hydrazones: Synthesis of alkene-functionalized oxindoles
-
A palladium-catalyzed cascade reaction of alkene-tethered carbamoyl chlorides with N-tosyl hydrazones is described. It provided a new way to synthesize various alkene-functionalized oxindoles bearing an all-carbon quaternary center. The olefin moieties co
- Sun, Wan,Chen, Chen,Qi, Yuan,Zhao, Jinghui,Bao, Yinwei,Zhu, Bolin
-
supporting information
p. 8358 - 8363
(2019/09/30)
-
- Lewis Acid Catalyzed [4 + 2] Cycloaddition of N-Tosylhydrazones with ortho-Quinone Methides
-
A formal [4 + 2] cycloaddition of N-tosylhydrazones with ortho-quinone methides was developed, affording the facile synthesis of diverse 1,3-oxazine derivatives under mild conditions. In this transformation, N-tosylhydrazones are used as a 1,2-dipole synt
- Wang, Chun-Ying,Han, Jia-Bin,Wang, Long,Tang, Xiang-Ying
-
p. 14258 - 14269
(2019/11/11)
-
- Rapid Synthesis of N-Tosylhydrazones under Solvent-Free Conditions and Their Potential Application Against Human Triple-Negative Breast Cancer
-
Some N-tosylhydrazone derivatives were effectively synthesized under solvent-free conditions by using a grinding method at room temperature. The short reaction time, clean and mild process with simple workup and easy purification of the target compounds w
- Xie, Zengyang,Song, Yuying,Xu, Lujia,Guo, Yukun,Zhang, Min,Li, Limei,Chen, Kai,Liu, Xue
-
p. 977 - 983
(2018/11/27)
-
- Pyrazole synthesis via a cascade Sonogashira coupling/cyclization of N-propargyl sulfonylhydrazones
-
An efficient approach for the preparation of pyrazoles via a Pd(ii)/Cu(i)-catalyzed Sonogashira coupling/cyclization of N-propargyl sulfonylhydrazones has been established. In this study, we firstly report the strategic use of a Sonogashira reaction to co
- Yang, Ying,Hu, Zi-Lin,Li, Ren-Hao,Chen, Yi-Hui,Zhan, Zhuang-Ping
-
supporting information
p. 197 - 201
(2018/01/17)
-
- Synthesis of 1,2-diarylethylenes by Pd-catalyzed one-pot reaction of benzyl halides, tosylhydrazide, and aryl aldehydes
-
Background: Substituted olefins are versatile functional groups and intermediates in chemistry, medicine, electronics, and optics and materials science fields because of their unique properties. One important class of substituted olefins 1,2-diarylethylenes have attracted considerable attention due to their presence in both natural products and pharmacologically active substances. Methods: In this paper, we developed a one-pot two-step coupling reaction of aryl aldehydes, tosylhydrazide with benzyl halides by using inexpensive Pd(PPh3)4 as catalyst, leading to a variety of 1,2- diphenylethenes derivatives with moderate to good yields. Results: The desired 1,2-diarylethylenes were obtained in 46-96% yields via Pd(0)-catalyzed one-pot reaction of benzyl halides, tosylhydrazide, and aryl aldehydes. Conclusion: The catalytic system presented here enables the use of easily accessible starting materials and good functional group tolerance.
- Shen, Xu,Liu, Ping,Liu, Yan,Dai, Bin
-
supporting information
p. 709 - 715
(2018/07/14)
-
- Ring-Opening of Indoles: An Unconventional Route for the Transformation of Indoles to 1 H-Pyrazoles Using Lewis Acid
-
An unusual transformation of indoles to pyrazoles via an aromatic ring-opening strategy has been developed. The salient feature of this strategy involves the C2-N1 bond opening and concomitant cyclization reaction of the C2=C3 bond of the indole moiety with the tosylhydrazone, which proceeds under transition-metal and ligand free conditions. This ring-opening functionalization of indoles provides a wide scope of differently substituted pyrazoles.
- Panda, Subhankar,Pradhan, Nirmalya,Manna, Debasis
-
supporting information
p. 573 - 578
(2018/09/25)
-
- One-Pot Acid-Catalyzed Ring-Opening/Cyclization/Oxidation of Aziridines with N-Tosylhydrazones: Access to 1,2,4-Triazines
-
A new, three-step, telescoped reaction sequence for the regioselective conversion of N-tosyl hydrazones and aziridines to 3,6-disubstituted and 3,5,6-trisubstituted 1,2,4-triazines is described. The process involves an efficient nucleophilic ring opening of the aziridine, giving access to a wide range of aminohydrazones, isolated with excellent yields. A “one-pot” procedure, combining the ring opening with a cyclization and an oxidation step, allows the preparation of diversified triazines in good yields.
- Crespin, Lorène,Biancalana, Lorenzo,Morack, Tobias,Blakemore, David C.,Ley, Steven V.
-
supporting information
p. 1084 - 1087
(2017/03/15)
-
- Highly stereoselective synthesis of 1-cyanocyclopropane-carboxamides from 3-substituted-2-cyanoacrylamides with N-tosylhydrazones under metal-free conditions
-
A metal-free cyclopropanation of electron-deficient olefins 3-substituted-2-cyanoacrylamides with N-tosylhydrazones has been successfully developed. This strategy provide a simple route to the synthesis of very valuable 1-cyanocyclopropanecarboxamides wit
- Nie, Xufeng,Wang, Yachuan,Yang, Lijun,Yang, Zaijun,Kang, Tairan
-
supporting information
p. 3003 - 3007
(2017/07/17)
-
- Metal-Free Ring-Expansion Reaction of Six-membered Sulfonylimines with Diazomethanes: An Approach toward Seven-Membered Enesulfonamides
-
A new metal-free, ring-expansion reaction of six-membered N-sulfonylimines with unstable diazomethanes, generated in situ from the N-tosylhydrazones, has been developed. This reaction delivers valuable seven-membered enesulfonamides by a Tiffeneau-Demjanov rearrangement and intramolecular proton transfer tautomerization process. Moreover, this ring-expansion reaction can be carried out in a one-pot fashion and scaled up to the gram scale by using aryl aldehydes, without the need to isolate the N-tosylhydrazone. A diazo thing: The title reaction between cyclic N-sulfonylimines and diazo compounds generated in situ from the N-tosylhydrazones is simple and functional-group tolerant. It thus delivers valuable seven-membered sulfonamides in up to 95 % yield. Moreover, this reaction can be carried out in one-pot starting from the aryl aldehydes, without the need to isolate the N-tosylhydrazone (right).
- Xia, An-Jie,Kang, Tai-Ran,He, Long,Chen, Lian-Mei,Li, Wen-Ting,Yang, Jin-Liang,Liu, Quan-Zhong
-
supporting information
p. 1441 - 1444
(2016/02/12)
-
- Iron(III) phthalocyanine-chloride-catalyzed synthesis of sulfones from sulfonylhydrazones
-
In this study, sulfones are synthesized from sulfonylhydrazones catalyzed by iron(III) phthalocyanine chloride. This reaction offers broad substrate scope, occurs under mild conditions, utilized readily available reactants, and forms products in good-to-h
- Zhao, Jun-Long,Guo, Shi-Huan,Qiu, Jun,Gou, Xiao-Feng,Hua, Cheng-Wen,Chen, Bang
-
supporting information
p. 2375 - 2378
(2016/05/19)
-
- Multicomponent Coupling Reactions of Two N-Tosyl Hydrazones and Elemental Sulfur: Selective Denitrogenation Pathway toward Unsymmetric 2,5-Disubstituted 1,3,4-Thiadiazoles
-
A copper-mediated, three-component reaction between two different N-Ts hydrazones and elemental sulfur was developed, leading to a series of unsymmetric 2,5-disubstituted 1,3,4-thiadiazoles in moderate yields with good functional group compatibility. This
- Zhou, Zhen,Liu, Yang,Chen, Jiangfei,Yao, En,Cheng, Jiang
-
supporting information
p. 5268 - 5271
(2016/10/31)
-
- Palladium-Catalyzed Intermolecular Carbene Insertion Prior to Intramolecular Heck Cyclization: Synthesis of 2-Arylidene-3-aryl-1-indanones
-
A domino process that converges the migratory insertion of carbene with a Heck reaction has been established as a versatile tool for the synthesis of 2-arylidene-3-aryl-1-indanones from very stable and easily accessible N-tosylhydrazones and 2′-iodochalco
- Arunprasath, Dhanarajan,Muthupandi, Pandi,Sekar, Govindasamy
-
supporting information
p. 5448 - 5451
(2015/11/18)
-
- NOVEL COMPOUNDS
-
Compounds of the formula (I), in which the substituents are as defined in claim 1, are suitable for use as nematicides.
- -
-
Paragraph 0378; 0379; 0380
(2015/01/07)
-
- Efficient synthesis of 1,5-disubstituted carbohydrazones using K 2CO3 as a carbonyl donor
-
A novel reaction that generates 1,5-disubstituted carbohydrazones via the carbonylation of tosylhydrazones has been developed. For the first time, the inexpensive, readily available, environmentally friendly, and nongaseous potassium carbonate is used as
- Wen, Jun,Yang, Chu-Ting,Jiang, Tao,Hu, Sheng,Yang, Tong-Zai,Wang, Xiao-Lin
-
supporting information
p. 2398 - 2401
(2014/05/20)
-
- An unprecedented approach to the Gabriel amine synthesis utilizing tosylhydrazones as alkylating agents
-
A new and one-pot version of the Gabriel phthalimide amine synthesis utilizing carbonyl compounds as alkylating agents via their tosylhydrazone surrogates is disclosed. The alkylation involves copper catalysed carbene insertion into the N-H bond of phthalimide. Basically, the protocol also offers a powerful tool for deoxygenative hydroamination of carbonyl compounds.
- Yadav, Arvind K.,Yadav, Lal Dhar S.
-
p. 34764 - 34767
(2014/11/08)
-
- NOVEL COMPOUNDS
-
Compounds of the formula (I), in which the substituents are as defined in claim 1, are suitable for use as nematicides.
- -
-
Page/Page column 90
(2013/08/28)
-
- A complementary approach to 3,5-substituted pyrazoles with tosylhydrazones and terminal alkynes mediated by TfOH
-
A complementary method for the preparation of 3,5-substituted pyrazoles in moderate to high yields has been explored via TfOH-induced addition of tosylhydrazones to the terminal alkynes. This acid-induced addition procedure might be an operationally safe alternative compared to typical 1,3-dipolar cycloaddition as there is no involvement of diazo compounds.
- Liu, Ping,Xu, Qian-Qian,Dong, Chao,Lei, Xinsheng,Lin, Guo-Qiang
-
supporting information
p. 2087 - 2092
(2012/11/07)
-
- Transition-metal-free synthesis of pinacol alkylboronates from tosylhydrazones
-
Highly efficient: Pinacol alkylboronates were synthesized by the reaction of tosylhydrazones with bis(pinacolato)diboron or pinacolborane under transition-metal-free conditions. This reaction represents an expeditious conversion of carbonyl functionality into a boronate group. Copyright
- Li, Huan,Wang, Long,Zhang, Yan,Wang, Jianbo
-
supporting information; experimental part
p. 2943 - 2946
(2012/04/18)
-
- An efficient one-pot synthesis of 3,5-disubstituted 1H-pyrazoles
-
An efficient, general, one-pot, three-component procedure for the preparation of 3,5-disubstituted 1H-pyrazoles via condensation of substituted aromatic aldehydes, tosylhydrazine and terminal alkynes in toluene is reported. The reaction tolerates a variety of functional groups and sterically hindered substrates to afford the desired pyrazoles in yields of 67-91%.
- Wu, Lei-Lei,Ge, Yi-Cen,He, Ting,Zhang, Lei,Fu, Xing-Li,Fu, Hai-Yan,Chen, Hua,Li, Rui-Xiang
-
experimental part
p. 1577 - 1583
(2012/06/29)
-
- Copper-catalyzed synthesis of alkylphosphonates from H-phosphonates and N-tosylhydrazones
-
A new catalytic system for the alkylation of H-phosphonates and diphenylphosphine oxide with N-tosylhydrazones has been developed. In the presence of copper(I) iodide and base, H-phosphonates react with N-tosylhydrazones to afford the corresponding coupled alkylphosphonates in good to excellent yields without any ligands. Alkylphosphonates can also be prepared in a one-pot process directly from carbonyl compounds without the isolation of tosylhydrazone intermediates.
- Miao, Wenjun,Gao, Yuzhen,Li, Xueqin,Gao, Yuxing,Tang, Guo,Zhao, Yufen
-
p. 2659 - 2664
(2013/01/15)
-
- Regioselectivity in the Addition of Singlet and Triplet Carbenes to 1,1-Dimethylallene. A Probe for Carbene Multiplicity
-
Singlet carbenes add preferentially to the more substituted bond of 1,1-dimethylallene (1), to give methylenecyclopropanes 3 as the major product.In contrast, many triplet carbenes add with differing regioselectivity, giving the thermodynamically preferre
- Creary, Xavier
-
p. 1611 - 1618
(2007/10/02)
-