- Cycloaddition Reactions of in situ Generated C2D2 in Dioxane: Efficient Synthetic Approach to D2-Labeled Nitrogen Heterocycles
-
In this work, an universal synthetic approach for the synthesis of D2-labeled nitrogen heterocycles based on cycloaddition reactions of in situ generated dideuteroacetylene is reported. A key feature of this method is the use of 1,4-dioxane as
- Voronin, Vladimir V.,Ledovskaya, Maria S.,Rodygin, Konstantin S.,Ananikov, Valentine P.
-
p. 5640 - 5648
(2021/11/11)
-
- [4 + 1] Annulation of in situ generated azoalkenes with amines: A powerful approach to access 1-substituted 1,2,3-triazoles
-
1-Substituted 1,2,3-triazoles represents ‘privileged’ structural scaffolds of many clinical pharmaceuticals. However, the traditional methods for their preparation mainly rely on thermal [3 + 2] cycloaddition of potentially dangerous acetylene and azides. Here we report a base-mediated [4 + 1] annulation of azoalkenes generated in situ from readily available difluoroacetaldehyde N-tosylhydrazones (DFHZ-Ts) with amines under relatively mild conditions. This azide- and acetylene-free strategy provides facile access to diverse 1-substituted 1,2,3-triazole derivatives in high yield in a regiospecific manner. This transformation has great functional group tolerance and can suit a broad substrate scope. Furthermore, the application of this novel methodology in the gram-scale synthesis of an antibiotic drug PH-027 and in the late-stage derivatization of several bioactive small molecules and clinical drugs demonstrated its generality, practicability and applicability.
- Bi, Xihe,Ning, Yongquan,Sivaguru, Paramasivam,Wang, Hongwei,Zanoni, Giuseppe
-
supporting information
(2021/09/30)
-
- The Hofmann reaction involving annulation of: O -(pyridin-2-yl)aryl amides selectively and rapidly leads to potential photocatalytically active 6 H -pyrido[1,2- c] quinazolin-6-one derivatives
-
A highly efficient PIFA-mediated Hofmann reaction of o-(pyridin-2-yl)aryl amides has been developed to selectively and rapidly construct various potential photocatalytically active 6H-pyrido[1,2-c]quinazolin-6-one derivatives. The use of a nontoxic and ec
- Gao, Wenjing,Liu, Tongxin,Wan, Yameng,Wu, Hao,Zhang, Guisheng,Zhang, Zhiguo
-
supporting information
p. 7955 - 7961
(2020/11/30)
-
- Microwave-assisted one-pot quick synthesis of 1-monosubstituted 1,2,3-triazoles from arylboronic acids, sodium azide and 3-butyn-2-ols
-
Abstract: Microwave-assisted one-pot quick synthesis to 1-monosubstituted 1,2,3-triazoles was achieved with good to excellent yields using the widely available arylboronic acids, sodium azide and 3-butyn-2-ols within 15 min. This method features high effi
- Du, Zhonglin,Li, Fenrui,Li, Li,Li, Ran
-
-
- An azide and acetylene free synthesis of 1-substituted 1,2,3-triazoles
-
This paper details a simple and efficient 3-component synthesis of 1-substituted 1,2,3-triazoles using a primary amine, 2,2-dimethoxyacetaldehyde and tosylhydrazide. The reaction proceeds in good to excellent yields using either aliphatic or aromatic amine substrates and is tolerant of a wide range of functional groups including electron-rich and deficient aryl groups, terminal alkynes, ketones and highly sterically encumbered amines.
- Patterson, Sarah J.M.,Clark, Peter R.,Williams, Glynn D.,Tomkinson, Nicholas C.O.
-
supporting information
(2020/10/13)
-
- Metal-Free Synthesis of Functional 1-Substituted-1,2,3-Triazoles from Ethenesulfonyl Fluoride and Organic Azides
-
The boom in growth of 1,4-disubstituted triazole products, in particular, since the early 2000’s, can be largely attributed to the birth of click chemistry and the discovery of the CuI-catalyzed azide–alkyne cycloaddition (CuAAC). Yet the synthesis of relatively simple, albeit important, 1-substituted-1,2,3-triazoles has been surprisingly more challenging. Reported here is a straightforward and scalable click-inspired protocol for the synthesis of 1-substituted-1,2,3-triazoles from organic azides and the bench stable acetylene surrogate ethenesulfonyl fluoride (ESF). The new transformation tolerates a wide selection of substrates and proceeds smoothly under metal-free conditions to give the products in excellent yield. Under controlled acidic conditions, the 1-substituted-1,2,3-triazole products undergo a Michael addition reaction with a second equivalent of ESF to give the unprecedented 1-substituted triazolium sulfonyl fluoride salts.
- Giel, Marie-Claire,Smedley, Christopher J.,Mackie, Emily R. R.,Guo, Taijie,Dong, Jiajia,Soares da Costa, Tatiana P.,Moses, John E.
-
supporting information
p. 1181 - 1186
(2019/12/11)
-
- Metal-free Semiconductor Photocatalysis for sp2 C?H Functionalization with Molecular Oxygen
-
Designing metal-free catalysts for solar energy conversion is a long-standing challenge in semiconductor photoredox catalysis (SPC). With visible-light-responsive hexagonal boron carbon nitride (h-BCN) as a non-metal photocatalyst, this system affords C?H/N?H coupling products with broad substitution tolerance and high efficiency with molecular oxygen as the terminal oxidant. The catalyst exhibits remarkable performance for the selective C?H functionalization of electron-rich arenes to C?N products (yields up to 95 %) and good stability (6 recycles). Both nitrogen heteroarenes and amine salts are competent coupling nucleophiles. Mechanically, the reactive oxygen species are superoxide anion radical (O2?.) and H2O2, which are proved by electron spin resonance (ESR) data, KI-starch, and control experiments. In addition, kinetic isotope effect (KIE) experiments indicate that C?H bond cleavage is not involved in the rate limiting step. This semiconductor-based photoredox system allows for C?H amination free of any metals, ligands, strong oxidants, and additives. It provides a complementary avenue to C?H functionalizations and enables synthetic applications efficiently in a sustainable manner.
- Zheng, Meifang,Ghosh, Indrajit,K?nig, Burkhard,Wang, Xinchen
-
p. 703 - 706
(2019/01/04)
-
- One-pot synthesis of 1-monosubstituted-1, 2, 3-triazoles from 2-methyl-3-butyn-2-ol
-
An efficient method for the synthesis of 1-monosubstituted-1, 2, 3-triazoles from 2-methyl-3-butyn-2-ol under copper catalyst conditions has been developed through a one-step one-pot sequence. This method provides a concise and efficient pathway to synthesize 1-monosubstituted-1, 2, 3-triazole derivatives in good to excellent yields.
- Liu, Yaowen,Han, Chunmei,Ma, Xinyuan,Yang, Jianhua,Feng, Xuepu,Jiang, Yubo
-
supporting information
p. 650 - 653
(2018/01/15)
-
- Phosphino-Triazole Ligands for Palladium-Catalyzed Cross-Coupling
-
Twelve 1,5-disubtituted and fourteen 5-substituted 1,2,3-triazole derivatives bearing diaryl or dialkyl phosphines at the 5-position were synthesized and used as ligands for palladium-catalyzed Suzuki-Miyaura cross-coupling reactions. Bulky substrates wer
- Zhao, Yiming,Van Nguyen, Huy,Male, Louise,Craven, Philip,Buckley, Benjamin R.,Fossey, John S.
-
supporting information
p. 4224 - 4241
(2018/10/25)
-
- One-Pot Synthesis of 1-Monosubstituted 1,2,3-Triazoles from Propargyl Alcohol
-
A one-pot synthesis of 1-monosubstituted-1,2,3-triazoles from propargyl alcohol and various aryl azides was achieved. This simple method provides concise and efficient access to various 1-monosubstituted 1,2,3-triazole derivatives through a three-step one
- Han, Chunmei,Dong, Suping,Zhang, Wensheng,Chen, Zhen
-
supporting information
p. 673 - 677
(2018/03/10)
-
- Copper(I) Oxide/N,N′-Bis[(2-furyl)methyl]oxalamide-Catalyzed Coupling of (Hetero)aryl Halides and Nitrogen Heterocycles at Low Catalytic Loading
-
An easily prepared oxalic diamide is a powerful ligand for the copper-catalyzed coupling of aryl halides with nitrogen heterocycles. Only 1–2 mol% each of copper(I) oxide and N,N′-bis[(2-furyl)methyl]oxalamide (BFMO) are needed to form N-arylation products under mild conditions. More than 10 different types of nitrogen heterocycles are compatible with these conditions, thereby giving the corresponding N-arylation products. (Figure presented.).
- Pawar, Govind Goroba,Wu, Haibo,De, Subhadip,Ma, Dawei
-
supporting information
p. 1631 - 1636
(2017/05/22)
-
- Searching for novel reusable biomass-derived solvents: Furfuryl alcohol/water azeotrope as a medium for waste-minimised copper-catalysed azide-alkyne cycloaddition
-
Herein, we report the first application of the furfuryl alcohol/water azeotrope as a sustainable and easily recoverable reaction medium in organic chemistry. The applicability of this novel medium was tested in copper-catalysed azide-alkyne cycloaddition
- Rasina, Dace,Lombi, Aurora,Santoro, Stefano,Ferlin, Francesco,Vaccaro, Luigi
-
supporting information
p. 6380 - 6386
(2017/09/25)
-
- N-terminal strategy (N1-N4) toward high performance liquid crystal materials
-
Liquid crystal materials have a variety of applications in many fields such as display techniques as well as photonics and optics. However, only few design principles have been disclosed on liquid crystal materials with different N-heterocycles as the terminal groups, which hinder the development of the heterocyclic liquid crystals. Here, a strategy of molecular design for N-heterocyclic liquid crystal materials is reported. On the basis of this strategy, a series of convenient N-heterocycles such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, 1,2,3,4-tetrazole were applied to synthesize the novel liquid crystals. Most of them have proved to exhibit good mesomorphic behaviors which make them excellent components in the mixture of the LCDs materials. The simple attachment of N-heterocyclic units to the liquid crystal molecules through a mild reaction condition will provide a good prospect for the design of N-heterocyclic liquid crystals.
- Hong, Fengying,Xia, Zhengce,Zhu, Dezhao,Wu, Hongxiang,Liu, Jianhui,Zeng, Zhuo
-
supporting information
p. 1285 - 1292
(2017/02/15)
-
- Hydrogenations at room temperature and atmospheric pressure with mesoionic carbene-stabilized borenium catalysts
-
1,2,3-Triazolylidene-based mesoionic carbene boranes have been synthesized in a convenient one-pot protocol from the corresponding 1,2,3-triazolium salts, base, and borane. Borenium ions are obtained by hydride abstraction and serve as catalysts in mild hydrogenation reactions of imines and unsaturated N-heterocycles at ambient pressure and temperature.
- Eisenberger, Patrick,Bestvater, Brian P.,Keske, Eric C.,Crudden, Cathleen M.
-
p. 2467 - 2471
(2015/02/19)
-
- Site-selective arene C-H amination via photoredox catalysis
-
Over the past several decades, organometallic cross-coupling chemistry has developed into one of the most reliable approaches to assemble complex aromatic compounds from preoxidized starting materials. More recently, transition metal-catalyzed carbon-hydrogen activation has circumvented the need for preoxidized starting materials, but this approach is limited by a lack of practical amination protocols. Here, we present a blueprint for aromatic carbon-hydrogen functionalization via photoredox catalysis and describe the utility of this strategy for arene amination. An organic photoredox-based catalyst system, consisting of an acridinium photooxidant and a nitroxyl radical, promotes site-selective amination of a variety of simple and complex aromatics with heteroaromatic azoles of interest in pharmaceutical research. We also describe the atom-economical use of ammonia to form anilines, without the need for prefunctionalization of the aromatic component.
- Romero, Nathan A.,Margrey, Kaila A.,Tay, Nicholas E.,Nicewicz, David A.
-
p. 1326 - 1330
(2015/10/12)
-
- Aromatic N-arylations catalyzed by copper-anchored porous zinc-based metal-organic framework under heterogeneous conditions
-
A highly porous Zn-based metal-organic framework (MOF) IRMOF-3 was covalently decorated with pyridine-2-aldehyde. The free amine group of IRMOF-3 upon condensation with pyridine-2-aldehyde affords a bidentate Schiff-base moiety in the porous matrix. The Schiff base moieties are availed to anchor copper(II) ions to display the catalyst's utility towards catalytic reactions. The catalyst was characterized by UV/Vis and IR spectroscopy, powder XRD spectrometry, SEM energy-dispersive X-ray spectrometry, and nitrogen sorption measurements. The catalyst exhibits excellent activity in catalyzing the N-arylation reaction of nitrogen-containing heterocycles with aryl bromides in DMSO medium, under mild condition (90°C) in the presence of Cs 2CO3. The porous catalyst demonstrates size selectivity towards substrate as a result of the presence of active sites inside the pores of the MOF. The anchored complex seems to be not leached or decomposed during the catalytic reactions up to five successive catalytic cycles, demonstrating practical advantages over homogeneous catalysis.
- Maity, Tanmoy,Saha, Debraj,Koner, Subratanath
-
p. 2373 - 2383
(2014/08/18)
-
- Synthesis of thermally stable energetic 1,2,3-triazole derivatives
-
Various thermally stable energetic polynitro-aryl-1,2,3-triazoles have been synthesized through Cu-catalyzed [3+2] cycloaddition reactions between their corresponding azides and alkynes, followed by nitration. These compounds were characterized by analyti
- Kumar, A. Sudheer,Ghule, Vikas D.,Subrahmanyam,Sahoo, Akhila K.
-
supporting information
p. 509 - 518
(2013/02/23)
-
- Preparation of polystyrene-supported vinyl sulfone and its application in the solid-phase organic synthesis of 1-monosubstituted 1,2,3-triazoles
-
A polystyrene-supported vinyl sulfone reagent was prepared and used for the solid-phase organic synthesis of 1-monosubstituted 1,2,3-triazoles via a 1,3-dipolar cycloaddition reaction with azides and subsequent cleavage from the polymer support through an elimination reaction in the presence of potassium tert-butoxide. The advantages of this method include straightforward operation, good yield and high purity of the crude products.
- Huang, Zhenzhong,Wang, Ruiling,Sheng, Shouri,Zhou, Ruyi,Cai, Mingzhong
-
p. 224 - 227
(2013/02/25)
-
- Green synthesis of 1-monosubstituted 1,2,3-triazoles via 'click chemistry' in water
-
The copper-catalyzed click reaction of organic azides with acetylene gas to give 1,2,3-triazoles using water as solvent was studied. The best yields are obtained in the presence of 10 mol% of CuI and 20 mol% of Et3N. Several 1-substituted triaz
- Wu, Luyong,Yan, Bo,Yang, Guo,Chen, Yuxue
-
p. 397 - 400
(2014/01/06)
-
- Facile one-pot synthesis of monosubstituted 1-aryl-1h-1,2,3-triazoles from arylboronic acids and prop-2-ynoic acid (=propiolic acid) or calcium acetylide (=calcium carbide) as acetylene source
-
The synthesis of monosubstituted 1-aryl-1H-1,2,3-triazoles was achieved in a one-pot reaction from arylboronic acids and prop-2-ynoic acid or calcium acetylide (=calcium carbide), respectively, as a source of acetylene, with yields ranging from moderate to excellent (Scheme 1, Table 2). The reaction conditions were successfully applied to arylboronic acids, including analogs with various functionalities. Unexpectedly, the 1,2,3-triazole moiety promoted a regioselective hydrodebromination (Scheme 2). Copyright
- Yang, Qing,Jiang, Yubo,Kuang, Chunxiang
-
experimental part
p. 448 - 454
(2012/05/04)
-
- Palladium-catalyzed direct arylation of heteroarenes with aryl mesylates
-
Not so challenging after all! The first general examples of the direct arylation of heteroarenes by using challenging aryl mesylates as electrophiles are disclosed. These easy reaction conditions also allow the functionalization of other heterocycles, such as caffeine, triazole and benzathiazole (see scheme). Copyright
- So, Chau Ming,Lau, Chak Po,Kwong, Fuk Yee
-
supporting information; experimental part
p. 761 - 765
(2011/03/20)
-
- A novel approach to 1-monosubstituted 1,2,3-triazoles by a click cycloaddition/decarboxylation process
-
The synthesis of 1-monosubstituted 1,2,3-triazoles was achieved using azides and propiolic acid by copper-catalyzed click cycloaddition/ decarboxylation, which was easily carried out in N,N-dimethylformamide at room temperature or 60 C with yields ranging
- Xu, Mei,Kuang, Chunxiang,Wang, Zhuo,Yang, Qing,Jiang, Yubo
-
supporting information; experimental part
p. 223 - 228
(2011/03/18)
-
- Facile and quick synthesis of 1-monosubstituted aryl 1,2,3-triazoles: A copper-free [3+2] cycloaddition
-
An efficient copper-free synthesis of 1-monosubstituted aryl 1,2,3-triazoles from sodium acetylide and aryl azides was developed, which was found suitable for various aryl azides and completed within 15 min at room temperature with moderate to excellent y
- Jiang, Yubo,Kuang, Chunxiang,Yang, Qing
-
experimental part
p. 289 - 292
(2011/02/28)
-
- Efficient synthesis of deuterated 1,2,3-triazoles
-
A wide variety of 1-monosubstituted 1,2,3-triazoles were synthesized efficiently via a copper-catalyzed click-reaction between azides and acetylene gas, generated in situ from CaC2 with the addition of H2O or D2O.
- Gonda, Zsombor,Lrincz, Krisztián,Novák, Zoltán
-
supporting information; experimental part
p. 6275 - 6277
(2011/01/04)
-
- Microwave irradiation as an effective means of synthesizing uninfstituted N-linked 1,2,3-triazoles from vinyl acetate and azides
-
N-Linked 1,2,3-triazoles have been prepared by a reaction of azides with vinyl acetate under microwave irradiation. Additionally, a microwave-assisted, two-step, one-pot procedure from halides involving azideinfstitution in diethyl ether, followed by -reaction with vinyl acetate, has effectively been employed. Georg Thieme Verlag Stuttgart - New York.
- Hansen, Signe Grann,Jensen, Henrik Helligs?
-
experimental part
p. 3275 - 3278
(2010/03/03)
-
- A convenient synthesis of 1-substituted 1,2,3-triazoles via CuI/Et 3N catalyzed 'click chemistry' from azides and acetylene gas
-
Copper(I)-catalyzed 'click chemistry' using acetylene gas was successfully explored under mild conditions. 1-Substituted-1,2,3-triazoles were conveniently synthesized from the corresponding aromatic and aliphatic azides. Georg Thieme Verlag Stuttgart.
- Wu, Lu-Yong,Xie, Yong-Xin,Chen, Zi-Sheng,Niu, Yan-Ning,Liang, Yong-Min
-
experimental part
p. 1453 - 1456
(2009/10/23)
-
- Monosubstituted 1,2,3-triazoles from two-step one-pot deprotection/click additions of trimethylsilylacetylene
-
Two-step one-pot reaction conditions have been developed for synthesizing 1-substituted-1,2,3-triazoles. This transformation involves the base-catalyzed deprotection of trimethylsilylacetylene followed by Cu-catalyzed Huisgen 1,3-dipolar cycloaddition under aqueous reaction conditions. Utilization of potassium carbonate as the base and methanol as the alcoholic aqueous co-solvent resulted in optimal yields of the desired products. The reaction conditions were found to be successful for both alkyl and aryl azide reactants, including analogs with electron-donating and electron-withdrawing functionality. This procedure stands as a simple and regioselective means by which to prepare 1-substituted-1,2,3-triazole compounds directly from azide precursors.
- Fletcher, James T.,Walz, Sara E.,Keeney, Matthew E.
-
scheme or table
p. 7030 - 7032
(2009/04/07)
-
- DECOMPOSITION OF ARYLAZIDES BY THF/n-BUTYLLITHIUM-II- -ISOLATION OF 1-ARYL-4,5-DIHYDRO-5-HYDROXY-1H-1,2,3-TRIAZOLES
-
By reaction of arylazides having no electron-withdrawing groups with the enolate ion of the acetaldehyde (formed by cycloreversion of THF in the presence of n-buthyllithium), 1-aryl-4,5-dihydro-5-hydroxy-1H-1,2,3-triazoles could be isolated and then characterized.Further reaction of such hydroxytriazolines with the same enolate ion afforded substantial amounts of the corresponding N-formylanilines , confirming their intermediacy in the previously reported decomposition of arylazides by THF/n-butyllithium.On the other hand, using alkoxides as bases, the preferred scheme of conversion of the hydroxytriazolines was found to be the known dehydration to 1-aryl-1H-1,2,3-triazoles.
- Nunno, L. Di,Scilimati, A.
-
p. 3913 - 3920
(2007/10/02)
-
- SITE SELECTIVITY IN THE REACTIONS OF 1,3-DIPOLES WITH NORBORNADIENE DERIVATIVES
-
The cycloadditions of arylazides, benzonitrile oxides and diphenylnitrile imine to norbornadiene derivatives 1a-c showed varying degree of site- and stereo-selectivity.With dipolarophile 1a arylazides and benzonitrile oxides attack, preferentially, the electron-poor tetrasubstituted double bond, while in the case of 1b and 1c is the substituted double bond which enters the cycloaddition.By contrast, 2-diazopropane and C-phenyl-N-methylnitrone react with the sole tetrasubstituted double bond of 1a-c in stereo- and site-specific cycloadditions.The quantitative evaluation of the two possible reaction paths was performed by glc analysis.The compounds detected were those arising from Diels-Alder cycloreversions of the thermally labile intermediate adducts 2 and 3 (Scheme 1).The results were rationalized on the basis of a qualitative perturbation treatment which considers frontier orbital interactions only.
- Cristina, D.,Amici, M. De,Micheli, C. De,Gandolfi, R.
-
p. 1349 - 1357
(2007/10/02)
-