Morpholine-mediated defluorinative cycloaddition of gem-difluoroalkenes and organic azides

• Tzu-Yu Huang,
• Mario Djugovski,
• Sweta Adhikari,
• Destinee L. Manning and
• Sudeshna Roy

Beilstein J. Org. Chem. 2023, 19, 1545–1554, doi:10.3762/bjoc.19.111

• process involves an attack of the organic azide nucleophile to the β-position of α-fluoronitroalkenes. The polarity of gem-difluoroalkenes is reversed in comparison to α-fluoronitroalkenes since the nucleophile attacks at the α-position of the gem-difluoroalkenes. A cycloaddition reaction between organic

• chemistry applications. In the reaction with piperidine, we observed unreacted organic azide 2b by TLC and 1H NMR analyses. Based on the 1H NMR analysis, 0.4 equiv of 2b had reacted to form the product, 0.9 equiv of 2b had decomposed to form aniline, and the remaining 0.2 equiv of 2b was unreacted

• with an organic azide. A relatively wide range of 1,4,5-trisubstituted-1,2,3-triazoles was obtained in 30–70% yields with high regioselectivity and modest functional group tolerability. This work demonstrates that gem-difluoroalkenes can serve as versatile fluorinated building blocks in lieu of alkynes

A recent overview on the synthesis of 1,4,5-trisubstituted 1,2,3-triazoles

• Pezhman Shiri,
• Ali Mohammad Amani and
• Thomas Mayer-Gall

Beilstein J. Org. Chem. 2021, 17, 1600–1628, doi:10.3762/bjoc.17.114

• irrespective of the nature and position of the substituent [39]. The supposed reaction mechanism for the reaction is shown in Scheme 3. Initially, the presence of bromine as an electron-withdrawing substituent lowers the LUMO energy to facilitate the cycloaddition process of acrolein with organic azide. The

• such as cinnamyl, (ethoxycarbonyl)methyl, 1-naphthalenemethyl, and (phenylthio)methyl were cyclized with ethynylstibanes 82 and diaryl diselenides 84 to afford the desired triazole products. The reaction between ethynylstibane, organic azide, and a range of diaryl diselenides 84 including sterically

• ) [55]. A probable mechanism for this transformation was proposed as illustrated in Scheme 29. The cycloaddition reaction between copper(I) acetylide 99 and organic azide 95 occurs to obtain the triazole cuprate intermediate 100, which reacts as a nucleophile with the disulfide electrophile 97 to

A systematic review on silica-, carbon-, and magnetic materials-supported copper species as efficient heterogeneous nanocatalysts in “click” reactions

• Pezhman Shiri and
• Jasem Aboonajmi

Beilstein J. Org. Chem. 2020, 16, 551–586, doi:10.3762/bjoc.16.52

• . Different ratios of Cu/Au (1:1, 3:1, and 5:1) were studied for the coupling reaction of a nonactivated terminal alkyne with an organic azide. Control measurements showed that 1:1 and 3:1 samples were more efficient than a 5:1 sample. The authors stated that increasing the Cu/Au ratio caused the formation of

Click chemistry towards thermally reversible photochromic 4,5-bisthiazolyl-1,2,3-triazoles

• Chenxia Zhang,
• Kaori Morinaka,
• Mahmut Kose,
• Takashi Ubukata and
• Yasushi Yokoyama

Beilstein J. Org. Chem. 2019, 15, 2161–2169, doi:10.3762/bjoc.15.213

• century, Sharpless and co-workers proposed the concept of “click chemistry” [14], which stands for the secure, quick, selective, general and facile reaction between two organic functional groups. In click chemistry, the Huisgen cyclization, which occurs between an organic azide and a terminal alkyne

• the organic azide we used commercially available benzyl azide. Since 1,2-bis(5-methyl-2-phenylthiazol-4-yl)ethyne was used in our previous research [32][33][34], we employed bisthiazolylethynes as the foundation for the skeleton of the target compounds. In order to examine the substituent effects of

Copper(I)-catalyzed tandem reaction: synthesis of 1,4-disubstituted 1,2,3-triazoles from alkyl diacyl peroxides, azidotrimethylsilane, and alkynes

• Muhammad Israr,
• Changqing Ye,
• Munira Taj Muhammad,
• Yajun Li and
• Hongli Bao

Beilstein J. Org. Chem. 2018, 14, 2916–2922, doi:10.3762/bjoc.14.270

• functionality of organic azide source. Moreover, as one of the most commonly appearing compounds in nature, carboxylic acids have rarely been directly used as the organic azide precursors for CuAAC reactions, considering the frequent involvement of organic halides. Thus, new methods with non or less toxic

• reagents and enriched organic azide sources for CuAAC reaction are still highly required. Herein, we report a novel CuAAC reaction, using aliphatic carboxylic acids as the alkyl source [36], and TMSN3 as the azide source (Scheme 1b). Because TMSN3 can react with alkynes to form the CuAAC reaction product

Recent applications of click chemistry for the functionalization of gold nanoparticles and their conversion to glyco-gold nanoparticles

• Vivek Poonthiyil,
• Thisbe K. Lindhorst,
• Vladimir B. Golovko and
• Antony J. Fairbanks

Beilstein J. Org. Chem. 2018, 14, 11–24, doi:10.3762/bjoc.14.2

• azide–alkyne Huisgen cycloaddition AuNP surface modification using NCAAC The azide–alkyne Huisgen cycloaddition (AAC) is a 1,3-dipolar cycloaddition between an organic azide and an alkyne that gives triazole products [37][38]. The non-catalysed azide–alkyne Huisgen cycloaddition (NCAAC) is very slow

• -stabilized AuNPs with thiol-linked sugar derivatives to obtain GAuNPs of various sizes. (c) Reactions of AuNPs (obtained after ligand exchange) with suitably functionalized sugar derivatives. The non-catalysed azide–alkyne Huisgen cycloaddition (NCAAC) between an organic azide (1,3-dipole) and an alkyne

Copper-catalyzed [3 + 2] cycloaddition of (phenylethynyl)di-p-tolylstibane with organic azides

• Mizuki Yamada,
• Mio Matsumura,
• Yuki Uchida,
• Masatoshi Kawahata,
• Yuki Murata,
• Naoki Kakusawa,
• Kentaro Yamaguchi and
• Shuji Yasuike

Beilstein J. Org. Chem. 2016, 12, 1309–1313, doi:10.3762/bjoc.12.123

• : cycloaddition; copper catalyst; ethynylstibane; organic azide; 1,2,3-triazole; Introduction The 1,3-dipolar azide–alkyne cycloaddition (AAC) has been effective for the synthesis of a wide variety of 1,2,3-triazoles [1]. However, this reaction has some limitations such as the requirement of high temperature and

• alkyne, an organic azide, and an H-phosphate in the presence of CuCl2 (10 mol %) and triethylamine (2 equiv) afforded the desired 1,2,3-triazolyl-5-phosphonates [23]. Fokin et al. carried out the reaction of ethynylbismuthane with organic azides using CuOTf (5 mol %) and isolated 5-bismuthano-1,2,3

• the reaction of the Cu(I) catalyst and ethynylstibane 1. Complex A coordinates with an organic azide to give complex B. Cyclization proceeds via a vinylidene-like transition state C to give 5-stibanotriazole 3. To test the reactivity of 5-stibanotriazole 3a was treated with hydrochloric acid, halogens

Synthesis of bi- and bis-1,2,3-triazoles by copper-catalyzed Huisgen cycloaddition: A family of valuable products by click chemistry

• Zhan-Jiang Zheng,
• Ding Wang,
• Zheng Xu and
• Li-Wen Xu

Beilstein J. Org. Chem. 2015, 11, 2557–2576, doi:10.3762/bjoc.11.276

• chose N-propargylpropiolamide 32 as the substrate and found the alkyne group with neighboring electron-withdrawing amide carbonyl was reacting exclusively with the organic azide under catalyst-free reaction conditions (with or without a solvent at room temperature) to give the mono-triazole intermediate

Synthesis of alpha-tetrasubstituted triazoles by copper-catalyzed silyl deprotection/azide cycloaddition

• Zachary L. Palchak,
• Paula T. Nguyen and
• Catharine H. Larsen

Beilstein J. Org. Chem. 2015, 11, 1425–1433, doi:10.3762/bjoc.11.154

• introduce a wide variety of substituents on 1,4-disubstituted 1,2,3-triazoles from the organic azide or terminal alkyne starting materials [1][2]. These Huisgen reactions [13] facilitate rapid drug screening by allowing for tracking in biological systems and the exploration of structure-activity

Sequential decarboxylative azide–alkyne cycloaddition and dehydrogenative coupling reactions: one-pot synthesis of polycyclic fused triazoles

• Kuppusamy Bharathimohan,
• Thanasekaran Ponpandian,
• A. Jafar Ahamed and
• Nattamai Bhuvanesh

Beilstein J. Org. Chem. 2014, 10, 3031–3037, doi:10.3762/bjoc.10.321

• cycloaddition, CuAAC) between an organic azide and a terminal alkyne is a well-established strategy for the construction of 1,4-disubstituted 1,2,3-triazoles [1][2][3][4]. In a recent development, this decarboxylative coupling reaction was well documented for the generation of C–C bonds [5]. This method has

A small azide-modified thiazole-based reporter molecule for fluorescence and mass spectrometric detection

• Stefanie Wolfram,
• Hendryk Würfel,
• Stefanie H. Habenicht,
• Christine Lembke,
• Phillipp Richter,
• Eckhard Birckner,
• Rainer Beckert and
• Georg Pohnert

Beilstein J. Org. Chem. 2014, 10, 2470–2479, doi:10.3762/bjoc.10.258

• reactive 4-hydroxy position is alkylated employing 1-bromo-3-chloropropane in acetone, yielding the chloropropyl ether 5 in a good yield (85%). The chlorine in compound 5 is subsequently exchanged using an excess of sodium azide in DMF at 80 °C for several hours, leading to the organic azide 1 in good

Thiophene-based donor–acceptor co-oligomers by copper-catalyzed 1,3-dipolar cycloaddition

• Stefanie Potratz,
• Amaresh Mishra and
• Peter Bäuerle

Beilstein J. Org. Chem. 2012, 8, 683–692, doi:10.3762/bjoc.8.76

• temperatures [33]. In order to overcome this inherent problem, we used a one-pot, two-step sequence, whereby an organic azide was generated in situ from a corresponding halide and immediately consumed in a reaction with copper acetylide [34][35][36]. Thus, as a model, we optimized the reaction of 2

EPR and pulsed ENDOR study of intermediates from reactions of aromatic azides with group 13 metal trichlorides

• Giorgio Bencivenni,
• Riccardo Cesari,
• Daniele Nanni,
• Hassane El Mkami and
• John C. Walton

Beilstein J. Org. Chem. 2010, 6, 713–725, doi:10.3762/bjoc.6.84

• also varied and several other azide types were included (Scheme 1). Each organic azide was reacted with the metal halide in dichloromethane/pentane or acetonitrile solution at rt, and an aliquot (~0.1 mL) was placed in a quartz capillary tube (diam 1 mm), purged with nitrogen for 15 min and transferred

Dimerization of propargyl and homopropargyl 6-azido- 6-deoxy- glycosides upon 1,3-dipolar cycloaddition

• Nikolas Pietrzik,
• Daniel Schmollinger and
• Thomas Ziegler

Beilstein J. Org. Chem. 2008, 4, No. 30, doi:10.3762/bjoc.4.30

• -triazoles which are known to be easily generated through a copper-catalyzed 1,3-dipolar cycloaddition of an organic azide and an alkynyl derivative (Click Reaction) [5][6][7]. For review articles on copper-catalyzed Click Reactions see references [8][9][10][11]. Recently, we applied this approach to a