- Potassium tert -Butoxide Promoted Synthesis of 4,5-Diaryl-2 H -1,2,3-triazoles from Tosylhydrazones and Nitriles
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Intermolecular cycloaddition of tosylhydrazones with nitriles was investigated. t -BuOK was shown to be an excellent base for increasing the effectiveness of the reaction in this protocol, and homocoupling of the tosylhydrazones was significantly inhibited by using xylene as a solvent. Through this transformation, a variety of 4,5-diaryl-2 H -1,2,3-triazoles were prepared in good to excellent yields and with high purities. The process is azide-free and transition-metal-free.
- Qiu, Shanguang,Chen, Yuxue,Song, Xinming,Liu, Li,Liu, Xi,Wu, Luyong
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supporting information
p. 86 - 90
(2020/11/02)
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- Mn(III)-mediated phosphinoylation of aldehyde hydrazones: Direct “one-pot” synthesis of α-iminophosphine oxides from aldehydes
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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
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supporting information
(2021/04/02)
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- Diversity-Oriented Synthesis of 1,2,4-Triazols, 1,3,4-Thiadiazols, and 1,3,4-Selenadiazoles from N-Tosylhydrazones
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The diversity-oriented synthesis of 1,2,4-triazols, 1,3,4-thiadiazols, and 1,3,4-selenadiazoles from N-tosylhydrazones was developed, and the reactions were general for a wide range of substrates, in which NH2CN, KOCN, KSCN, and KSeCN were used as odorless sources. Two different pathways were proposed, and N-tosylhydrazonoyl chlorides were formed in situ in the presence of NCS.
- Wei, Zeyang,Zhang, Qi,Tang, Meng,Zhang, Siyu,Zhang, Qian
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supporting information
p. 4436 - 4440
(2021/05/26)
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- Selective hydrolysis of phosphorus(v) compounds to form organophosphorus monoacids
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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
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p. 6007 - 6014
(2021/07/21)
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- Visible-Light-Catalyzed in Situ Denitrogenative Sulfonylation of Sulfonylhydrazones
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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
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supporting information
p. 6784 - 6788
(2021/09/08)
-
- Palladium-Catalyzed Three-Component Coupling Reaction of o-Bromobenzaldehyde, N-Tosylhydrazone, and Methanol
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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
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supporting information
p. 2087 - 2092
(2020/03/04)
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- Blue Light-promoted Carbene Transfer Reactions of Tosylhydrazones
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Metal-free photochemical carbene-transfer reactions of tosylhydrazones were developed under blue light irradiation at room temperature. This reaction constructs C?X (X=C, N, O, S) bonds and cyclopropanes from readily available and stable starting material
- Xu, Yingying,Lv, Guanghui,Yan, Kaichuan,He, Hua,Li, Jianglian,Luo, Yi,Lai, Ruizhi,Hai, Li,Wu, Yong
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supporting information
p. 1945 - 1947
(2020/06/08)
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- Acid-Promoted [3 + 1 + 1] Cyclization of N-Tosylhydrazones and Isocyanides: A Method for the Preparation of 4,5-Diaminopyrazoles
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A facile method for the preparation of 4,5-diaminopyrazoles from N-tosylhydrazones and isocyanides was developed. The reaction was general for a wide range of substrates, and it demonstrated excellent tolerance to a variety of substituents. More important
- Zhang, Qian,Tang, Meng,Zhang, Siyu,Wei, Zeyang
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supporting information
p. 5182 - 5186
(2020/07/04)
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- Photoisomerization-enhanced 1,3-dipolar cycloaddition of carbon-bridged octocyclic azobenzene with photo-released nitrile imine for peptide stapling and imaging in live cells
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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
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supporting information
p. 5602 - 5607
(2020/08/21)
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- Copper-catalyzed cross-coupling and sequential allene-mediated cyclization for the synthesis of 1,2,3-triazolo[1,5-a]quinolines
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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
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supporting information
p. 7174 - 7182
(2020/10/02)
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- One-Pot Reaction between N-Tosylhydrazones and 2-Nitrobenzyl Bromide: Route to NH-Free C2-Arylindoles
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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
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p. 228 - 238
(2019/01/04)
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- Lewis Acid Catalyzed [4 + 2] Cycloaddition of N-Tosylhydrazones with ortho-Quinone Methides
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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
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p. 14258 - 14269
(2019/11/11)
-
- 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
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supporting information
(2019/05/08)
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- Substituent-Oriented Synthesis of Substituted Pyrazoles/Chromeno[3,2- c]pyrazoles via Sequential Reactions of Chromones/3-Chlorochromones and Tosylhydrazones
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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
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p. 5913 - 5921
(2019/05/10)
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- Selective C?C Coupling of Vinyl Epoxides with Diborylmethide Lithium Salts
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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
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supporting information
p. 8013 - 8017
(2019/05/29)
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- 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
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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
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- Rapid Synthesis of N-Tosylhydrazones under Solvent-Free Conditions and Their Potential Application Against Human Triple-Negative Breast Cancer
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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
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p. 977 - 983
(2018/11/27)
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- Pyrazole synthesis via a cascade Sonogashira coupling/cyclization of N-propargyl sulfonylhydrazones
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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
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supporting information
p. 197 - 201
(2018/01/17)
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- Direct Aryloxylation/Alkyloxylation of Dialkyl Phosphonates for the Synthesis of Mixed Phosphonates
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A strategy for the direct functionalization strategy of inertial dialkyl phosphonates with hydroxy compounds to afford diverse mixed phosphonates with good yields and functional-group tolerance has been developed. Mechanistic investigations involving both NMR studies and DFT studies suggest that an unprecedented highly reactive PV species (phosphoryl pyridin-1-ium salt), a key intermediate for this new synthetic transformation, is generated in situ from dialkyl phosphonate in the presence of Tf2O/pyridine.
- Huang, Hai,Denne, Johanna,Yang, Chou-Hsun,Wang, Haobin,Kang, Jun Yong
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supporting information
p. 6624 - 6628
(2018/05/14)
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- Synthesis of 1,2-diarylethylenes by Pd-catalyzed one-pot reaction of benzyl halides, tosylhydrazide, and aryl aldehydes
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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
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supporting information
p. 709 - 715
(2018/07/14)
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- Ring-Opening of Indoles: An Unconventional Route for the Transformation of Indoles to 1 H-Pyrazoles Using Lewis Acid
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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
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supporting information
p. 573 - 578
(2018/09/25)
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- Asymmetric radical cyclopropanation of alkenes with in situ-generated donor-substituted diazo reagents via Co(II)-based metalloradical catalysis
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Donor-substituted diazo reagents, generated in situ from sulfonyl hydrazones in the presence of base, can serve as suitable radical precursors for Co(II)-based metalloradical catalysis (MRC). The cobalt(II) complex of D2-symmetric chiral porphyrin [Co(3,5-DuBu-Xu(2'-Naph)Phyrin)] is an efficient metalloradical catalyst that is capable of activating different N-arylsulfonyl hydrazones for asymmetric radical cyclopropanation of a broad range of alkenes, affording the corresponding cyclopropanes in high yields with effective control of both diastereo- and enantioselectivity. This Co(II)-based metalloradical system represents the first catalytic protocol that can effectively utilize donor-type diazo reagents for asymmetric olefin cyclopropanation.
- Wang, Yong,Wen, Xin,Cui, Xin,Wojtas, Lukasz,Zhang, X. Peter
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supporting information
p. 1049 - 1052
(2017/05/15)
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- One-Pot Acid-Catalyzed Ring-Opening/Cyclization/Oxidation of Aziridines with N-Tosylhydrazones: Access to 1,2,4-Triazines
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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.
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supporting information
p. 1084 - 1087
(2017/03/15)
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- Synthesis of Di- and Triarylmethanes through Palladium-Catalyzed Reductive Coupling of N -Tosylhydrazones and Aryl Bromides
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A palladium-catalyzed reductive coupling between N-tosylhydrazones and aryl bromides has been developed. The reaction provides an efficient method for the synthesis of diarylmethanes and triarylmethanes via the formation of C(sp2)-C(sp3) single bonds. This new methodology for the synthesis of diarylmethanes and triarylmethanes is featured by the ready availability of the starting materials, mild reaction conditions, and the tolerance of wide range of functional groups. The reaction follows a pathway including palladium carbene formation, migratory insertion, and reduction of the alkylpalladium(II) intermediate.
- Xia, Yamu,Hu, Fangdong,Xia, Ying,Liu, Zhenxing,Ye, Fei,Zhang, Yan,Wang, Jianbo
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p. 1073 - 1086
(2017/02/24)
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- Synthesis of Benzyltributylstannanes by the Reaction of N-Tosylhydrazones with Bu3SnH
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An efficient stannylation process with N-tosylhydrazones or directly with carbonyl compounds has been developed. A series of functionalized benzyl- and alkyltributylstannanes can be synthesized in moderate to good yields under transition-metal-free conditions. Tandem transformations involving stannylation/Stille cross-coupling reaction have been carried out without purification of the benzyltributylstannane intermediates to afford a series of diarylmethane derivatives.
- Qiu, Di,Wang, Shuai,Meng, He,Tang, Shengbo,Zhang, Yan,Wang, Jianbo
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p. 624 - 632
(2017/04/26)
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- Highly stereoselective synthesis of 1-cyanocyclopropane-carboxamides from 3-substituted-2-cyanoacrylamides with N-tosylhydrazones under metal-free conditions
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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
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supporting information
p. 3003 - 3007
(2017/07/17)
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- The microwave-assisted ortho-alkylation of azine N-oxides with N-tosylhydrazones catalyzed by copper(i) iodide
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A copper catalyzed regioselective cross-coupling of N-tosylhydrazones with azine N-oxides to yield ortho-alkylated products in moderate to good yields is reported. The reaction is facilitated by microwave, takes place without any ligand, and uses inexpensive copper(i) iodide as the catalyst.
- Jha, Abadh Kishor,Jain, Nidhi
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p. 1831 - 1834
(2016/02/05)
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- Synthesis and antimicrobial evaluation of hydrazones derived from 4-methylbenzenesulfonohydrazide in aqueous medium
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A series of biologically active N′-substituted-4-methylbenzenesulfonohydrazide derivatives were synthesized by condensation of 4-methylbenzenesulfonohydrazide and aromatic carbonyl compounds in the presence of polystyrene sulfonic acid in aqueous medium.
- Ghiya, Sunita,Joshi, Yogesh C.
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p. 970 - 976
(2016/04/20)
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- Metal-Free Ring-Expansion Reaction of Six-membered Sulfonylimines with Diazomethanes: An Approach toward Seven-Membered Enesulfonamides
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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
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supporting information
p. 1441 - 1444
(2016/02/12)
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- Iron(III) phthalocyanine-chloride-catalyzed synthesis of sulfones from sulfonylhydrazones
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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)
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- Multicomponent Coupling Reactions of Two N-Tosyl Hydrazones and Elemental Sulfur: Selective Denitrogenation Pathway toward Unsymmetric 2,5-Disubstituted 1,3,4-Thiadiazoles
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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)
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- Copper(I)-Catalyzed Alkylation of Polyfluoroarenes through Direct C - H Bond Functionalization
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The copper(I)-catalyzed alkylation of electron-deficient polyfluoroarenes with N-tosylhydrazones and diazo compounds has been developed. This reaction uses readily available starting materials and is operationally simple, thus representing a practical method for the construction of C(sp2) - C(sp3) bonds with polyfluoroarenes through direct C - H bond functionalization. Mechanistically, copper(I) carbene formation and subsequent migratory insertion are proposed as the key steps in the reaction pathway.
- Xu, Shuai,Wu, Guojiao,Ye, Fei,Wang, Xi,Li, Huan,Zhao, Xia,Zhang, Yan,Wang, Jianbo
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supporting information
p. 4669 - 4672
(2015/04/14)
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- Pd-Catalyzed Highly Regio- and Stereoselective Formation of C-C Double Bonds: An Efficient Method for the Synthesis of Benzofuran-, Dihydrobenzofuran-, and Indoline-Containing Alkenes
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A highly regio- and stereoselective C-C double bond formation reaction via Pd-catalyzed Heck-type cascade process with N-tosylhydrazones has been developed. Various N-tosylhydrazones derived from both ketones and aldehydes are found to be efficient substrates to provide di- and trisubstituted olefins with high regio- and stereoselectivity. Furthermore, this reaction has a good functional group tolerance and different benzofuran-, dihydrobenzofuran-, and indoline-containing alkene products were obtained with high selectivity.
- Gao, Yang,Xiong, Wenfang,Chen, Huoji,Wu, Wanqing,Peng, Jianwen,Gao, Yinglan,Jiang, Huanfeng
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p. 7456 - 7467
(2015/08/18)
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- Synthesis of terminal allenes through copper-mediated cross-coupling of ethyne with N-tosylhydrazones or α-diazoesters
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Ethyne is employed as coupling partner in coppermediated cross-coupling reactions with N-tosylhydrazones and α-diazoacetate, leading to the development of a new synthetic method for terminal allenes. With this novel coupling method, the terminal allenes w
- Ye, Fei,Wang, Chengpeng,Ma, Xiaoshen,Hossain, Mohammad Lokman,Xia, Ying,Zhang, Yan,Wang, Jianbo
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p. 647 - 652
(2016/09/12)
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- Palladium-Catalyzed Intermolecular Carbene Insertion Prior to Intramolecular Heck Cyclization: Synthesis of 2-Arylidene-3-aryl-1-indanones
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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
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supporting information
p. 5448 - 5451
(2015/11/18)
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- Copper(I)-Catalyzed Reductive Cross-Coupling of N-Tosylhydrazones with Amides: A Straightforward Method for the Construction of C(sp3)- N Amide Bonds from Aldehydes
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A method for the one-pot synthesis of substituted amides from aldehydes and amides is presented. Namely, condensation of aldehydes with N-tosylhydrazide generated the N-tosylhydrazones which were then reductively cross-coupled in situ with primary or secondary amides in the presence of a copper catalyst to afford secondary or tertiary amides, respectively. The reaction proceeded efficiently for a wide range of aldehydes and amides under the optimized conditions, i.e., 10 mol% of tetrakis(acetonitrile)copper(I) tetrafluoroborate [Cu(CH3CN)4BF4], 1 mol% of tetra-n-butylammonium iodide [(n-Bu)4NI], and sodium hydroxide [NaOH] as base in tetrahydrofuran (THF) at 80 C. As a result, the method provides a straightforward route for the synthesis of substituted amides from readily available aldehydes via a transition metal-catalyzed C(sp3)- N amide bond forming reaction.
- Xu, Peng,Han, Fu-She,Wang, Yan-Hua
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supporting information
p. 3441 - 3446
(2016/01/25)
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- Regioselective synthesis of 1,3,5-Trisubstituted Pyrazoles from N-Alkylated Tosylhydrazones and terminal Alkynes
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An efficient synthesis of 1,3,5-trisubstituted pyrazoles from Nalkylated tosylhydrazones and terminal alkynes was developed. The protocol was applied to a wide range of substrates and demonstrated excellent tolerance to a variety of substituents, includin
- Kong, Yuanfang,Tang, Meng,Wang, Yun
-
supporting information
p. 576 - 579
(2014/04/03)
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- Base-catalyzed N -N bond cleavage of hydrazones: Synthesis of α-amino ketones
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An efficient Cs2CO3-promoted synthesis of α-amino ketones using hydrazines, aldehydes, and α-haloketones as starting materials through a cascade condensation/nucleophilic substitution/N -N bond cleavage route is developed. The carbonyl group plays a key role in this novel N -N bond cleavage process. Breaking good: A novel method of base-catalyzed N -N bond cleavage of hydrazones has been discovered. A variety of α-amino ketones was synthesized using hydrazines, α-haloketones, and benzaldehyde as starting materials through a cascade condensation/ nucleophilic substitution/N -N bond cleavage sequence.
- Tang, Hai-Tao,Zhou, Yun-Bing,Zhu, Yu,Sun, Hong-Chao,Lin, Min,Zhan, Zhuang-Ping
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supporting information
p. 1278 - 1281
(2014/05/06)
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- Efficient synthesis of 1,5-disubstituted carbohydrazones using K 2CO3 as a carbonyl donor
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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
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supporting information
p. 2398 - 2401
(2014/05/20)
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- An unprecedented approach to the Gabriel amine synthesis utilizing tosylhydrazones as alkylating agents
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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.
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p. 34764 - 34767
(2014/11/08)
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- Reductive coupling reactions: A new strategy for C(sp3)-P bond formation
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The C(sp3)-P bond forming reaction utilizing N-tosylhydrazones as readily available alkylating reagents was developed, which provides a new opportunity for preparing phosphine oxide derivatives with moderate to good yields. This reductive coupling reaction is proposed to proceed through an insertion of copper carbene into P-H bond of H-phosphorus oxides. The salient features of the reaction are operational simplicity and functional-group tolerance.
- Chen, Zi-Sheng,Zhou, Zhao-Zhao,Hua, Hui-Liang,Duan, Xin-Hua,Luo, Jian-Yi,Wang, Jia,Zhou, Ping-Xin,Liang, Yong-Min
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supporting information
p. 1065 - 1068
(2013/02/25)
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- An efficient one-pot synthesis of 3,5-diaryl-4-bromopyrazoles by 1,3-dipolar cycloaddition of in situ generated diazo compounds and 1-bromoalk-1-ynes
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A simple, highly efficient, one-pot synthesis of 3,5-di-aryl-4- bromopyrazoles via 1,3-dipolar cycloaddition of diazo compounds and alkynyl bromides has been developed. The diazo compounds and alkynyl bromides were generated in situ from tosylhydrazones and gem-dibromoalkenes, respectively. When ketone-derived hydrazones were used, 3,5-diaryl-4-bromo-3H-pyrazoles were obtained and the isomerization products 3,5-diaryl-4-bromo-1H-pyrazoles were formed when using aldehyde-derived hydrazones. The reaction system exhibited high regioselectivity and good functional group tolerance. Both electron-rich and electron-deficient-substituents on the aromatic ring of the hydrazones or the gem-dibromoalkenes gave desired products in moderate to good yields (67-86%). Georg Thieme Verlag Stuttgart - New York.
- Sha, Qiang,Wei, Yunyang
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supporting information
p. 413 - 420
(2013/03/14)
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- Copper-catalyzed direct ortho-alkylation of N-iminopyridinium ylides with N-tosylhydrazones
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Copper-catalyzed cross-coupling of N-tosylhydrazones with N-iminopyridinium ylides leads to the direct C-H alkylation. This direct C-H bond alkylation transformation uses inexpensive CuI as the catalyst without any ligand. The reaction is operationally simple and conducted under mild conditions, giving the corresponding alkylated pyridines in moderate to good yields. DFT calculation provides insights into the reaction mechanism, suggesting that the reaction proceeds through the Cu carbene migratory insertion process.
- Xiao, Qing,Ling, Lin,Ye, Fei,Tan, Renchang,Tian, Leiming,Zhang, Yan,Li, Yuxue,Wang, Jianbo
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supporting information
p. 3879 - 3885
(2013/05/22)
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- N-Alkylation of tosylhydrazones in the presence of triphenylphosphine
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An efficient N-alkylation reaction of tosylhydrazones was developed in the presence of triphenylphosphine; triphenylphosphine played a key role in the transformation. A range of N-alkylated tosylhydrazones were prepared in good to high yields.
- Kong, Yuanfang,Zhang, Wen,Tang, Meng,Wang, Haiming
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supporting information
p. 7487 - 7491
(2013/08/23)
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- Synthesis of allyl allenes through three-component cross-coupling reaction of N-tosylhydrazones, terminal alkynes, and allyl halides
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Three's a crowd: Tri- and tetrasubstituted allyl allenes can be easily accessed by this CuI-catalyzed three-component coupling reaction of N-tosylhydrazones, terminal alkynes, and allyl halides. The reaction proceeds through a mechanism involving copper carbene migratory insertion.
- Ye, Fei,Hossain, Mohammad Lokman,Xu, Yan,Ma, Xiaoshen,Xiao, Qing,Zhang, Yan,Wang, Jianbo
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supporting information
p. 1404 - 1407
(2013/07/26)
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- Microwave assisted efficient aminocarbonylation of N-tosylhydrazones with molybdenum hexacarbonyl and amines
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An efficient aminocarbonylation of N-tosylhydrazones derived from aromatic aldehydes and ketones mediated by molybdenum hexacarbonyl is reported. This method is palladium-free and provides a rapid access to the α-aryl acetamides in moderate to good yields.
- Rao, K. Penta,Basak, Ashok K.,Raju, Amancha,Patil, Vikas S.,Reddy, L. Krishnakanth
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supporting information
p. 5510 - 5513
(2013/09/23)
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- DABCO-promoted synthesis of pyrazoles from tosylhydrazones and nitroalkenes
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An efficient synthesis of pyrazoles from tosylhydrazones and nitroalkenes was developed. In comparison with the previously reported 1,3-dipolar cycloaddition reaction of diazo compounds with electron-deficient alkenes or alkynes, this methodology proceeded with a sequential Baylis-Hillman/ intramolecular cyclization mechanism and a variety of reversed regioselectivity products were prepared in good yields.
- Tang, Meng,Zhang, Wen,Kong, Yuanfang
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supporting information
p. 6250 - 6254
(2013/09/23)
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- Synthesis of substituted 1 H-indazoles from arynes and hydrazones
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The 1H-indazole skeleton can be constructed by a [3 + 2] annulation approach from arynes and hydrazones. Under different reaction conditions, both N-tosylhydrazones and N-aryl/alkylhydrazones can be used to afford a variety of indazoles. The former reaction affords 3-substituted indazoles either via in situ generated diazo compounds or through an annulation/elimination process. The latter reaction leads to 1,3-disubstituted indazoles likely through an annulation/oxidation process. The reactions operate under mild conditions and can accommodate aryl, vinyl, and less satisfactorily, alkyl groups.
- Li, Pan,Wu, Chunrui,Zhao, Jingjing,Rogness, Donald C.,Shi, Feng
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experimental part
p. 3149 - 3158
(2012/07/14)
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- A complementary approach to 3,5-substituted pyrazoles with tosylhydrazones and terminal alkynes mediated by TfOH
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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
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supporting information
p. 2087 - 2092
(2012/11/07)
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- Transition-metal-free synthesis of pinacol alkylboronates from tosylhydrazones
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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
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supporting information; experimental part
p. 2943 - 2946
(2012/04/18)
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