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Design and Synthesis of New 5-Aryl-4-Arylethynyl-1H-1,2,3-Triazoles with Valuable Photophysical and Biological Properties

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Design and Synthesis of New 5-Aryl-4-Arylethynyl-1H-1,2,3-Triazoles with Valuable Photophysical and Biological Properties molecules Article Design and Synthesis of New 5-aryl-4-Arylethynyl-1H-1,2,3-triazoles with Valuable Photophysical and Biological Properties Mariia M. Efremova 1 , Anastasia I. Govdi 1,* , Valeria V. Frolova 2 , Andrey M. Rumyantsev 3 and Irina A. Balova 1,* 1 Institute of Chemistry, Saint Petersburg State University (SPbU), Universitetskaya nab. 7/9, 199034 Saint Petersburg, Russia; [email protected] 2 Department of Pharmaceutical Chemistry, Saint Petersburg State Chemical Pharmaceutical University (SPCPU), 14A Professor Popov Str., 197376 Saint Petersburg, Russia; [email protected] 3 Department of Genetics and Biotechnology, Saint Petersburg State University (SPbU), Universitetskaya nab. 7/9, 199034 Saint Petersburg, Russia; [email protected] * Correspondence: [email protected] (A.I.G.); [email protected] (I.A.B.); Tel.: +7-812-428-4054 (A.I.G.); +7-812-428-6733 (I.A.B.) Abstract: Cu-catalyzed 1,3-dipolar cycloaddition of methyl 2-azidoacetate to iodobuta-1,3-diynes and subsequent Suzuki-Miyaura cross-coupling were used to synthesize new triazoles derivatives: 5- aryl-4-arylethynyl-1H-1,2,3-triazoles. Investigation of their optical properties by using UV absorption and fluorescence emission spectroscopies revealed that all molecules possess fluorescence properties Citation: Efremova, M.M.; with the values of the Stokes shift more than 100 nm. The photophysical behavior of the two most Govdi, A.I.; Frolova, V.V.; promising triazoles in polar and non-polar solvents was also studied. Rumyantsev, A.M.; Balova, I.A. Design and Synthesis of New 5-aryl-4- Keywords: 1,2,3-triazoles; 1,3-diynes; azide–alkyne cycloaddition; Suzuki-Miyaura cross-coupling; Arylethynyl-1H-1,2,3-triazoles with Valuable Photophysical and fluorescence; solvatochromism; antimicrobial activity; cytotoxity Biological Properties. Molecules 2021, 26, 2801. https://doi.org/10.3390/ molecules26092801 1. Introduction Academic Editor: Gianfranco Favi In recent years, 1H-1,2,3-Triazoles are of increasing interest to researchers as one of the most promising classes of heterocyclic compounds for different purposes of bioconjugation [1] Received: 19 April 2021 design of new catalysts [2], supramolecular ensembles [3,4], and polymeric materials [5]. 1,2,3- Accepted: 4 May 2021 Triazoles are widely synthetically available compounds due to the development of simple Published: 10 May 2021 and effective methods of their preparation on the base of “click” reaction of Cu-catalyzed azide–alkyne cycloaddition (CuAAC) [6–10]. Due to the wide range of available derivatives Publisher’s Note: MDPI stays neutral and the accessibility of structural modifications by a variety of pharmacophore fragments 1,2,3- with regard to jurisdictional claims in triazoles attract a special interest in the field of drug design [11–14]. The biological properties published maps and institutional affil- of triazole derivatives are very diverse. Currently, among the most widely studied types of iations. activity are: antibacterial [14,15], antiviral [16], and anticancer [17,18]. Today, a new field of application of triazoles is rapidly developing—using as dyes and fluorophores [19]. For example, CuAAC can be used in the design of push–pull dyes for the formation of triazole linker to connect electron-donating and electron-withdrawing parts of Copyright: © 2021 by the authors. the molecule [20–22], in particular, for the synthesis of dyes possessing luminescent proper- Licensee MDPI, Basel, Switzerland. ties [23]. It has been shown previously that the luminescent parameters, such as absorption This article is an open access article minimum and maximum, Stokes sifts, and quantum yields for triazole derivatives are distributed under the terms and strongly dependent on the mutual arrangement of substituents in the triazole ring [24–26]. conditions of the Creative Commons For some of the compounds, the dependence of fluorescent properties on the solvent was Attribution (CC BY) license (https:// demonstrated [27–29]. However, a limitation of the classical CuAAC method is that the creativecommons.org/licenses/by/ necessity to use terminal acetylenes leads to the possibility of changing substituents only 4.0/). Molecules 2021, 26, 2801. https://doi.org/10.3390/molecules26092801 https://www.mdpi.com/journal/molecules Molecules 2021, 26, x FOR PEER REVIEW 2 of 15 Molecules 2021, 26, 2801 2 of 14 substituents only in the first and fourth positions of the triazole ring. The substituents in inthese the positions first and fourthare not positions in direct π‐ ofconjugation the triazole to ring. each The other; substituents however, in formal these cross positions‐con‐ arejugation not in through direct π the-conjugation triazole system to each can other; be recognized however, formalfor them. cross-conjugation Also, triazole derivatives through thecan triazolebe used system as chemosensors can be recognized for metal for cations them. due Also, to the triazole combination derivatives of photophysical can be used asproperties chemosensors with an for ability metal to cations form complexes due to the due combination to the presence of photophysical of lone electron properties pairs at withnitrogen an ability atoms to [30,31]. form complexesAt the same due time, to 4 the‐ethynyl presence‐1H‐ of1,2,3 lone‐triazole electron moiety pairs was at nitrogen not pre‐ H atomsviously [30 used,31]. as At a thelinker same for time,fluorophores. 4-ethynyl-1 -1,2,3-triazole moiety was not previously used as a linker for fluorophores. 5‐Iodo‐1H‐1,2,3‐triazoles are one of the most promising classes of triazole derivatives 5-Iodo-1H-1,2,3-triazoles are one of the most promising classes of triazole derivatives due to the possibility of caring out in a wide range of C‐I functionalization reactions [32]. due to the possibility of caring out in a wide range of C-I functionalization reactions [32]. These compounds are also easily available due to CuAAC, then the 1‐idoacetylenes are These compounds are also easily available due to CuAAC, then the 1-idoacetylenes are used instead of terminal acetylenes [33,34]. Earlier, the possibility to involve 1‐iodobuta‐ used instead of terminal acetylenes [33,34]. Earlier, the possibility to involve 1-iodobuta- 1,3‐diynes in CuAAC and modification of obtained 4‐ethynyl‐5‐iodo‐1,2,3‐iodotriazoles 1,3-diynes in CuAAC and modification of obtained 4-ethynyl-5-iodo-1,2,3-iodotriazoles in in cross‐coupling reactions were shown by our research group [35]. cross-coupling reactions were shown by our research group [35]. Herein we report the design and synthesis of new 5‐aryl‐4‐arylethynyl‐1H‐1,2,3‐tria‐ Herein we report the design and synthesis of new 5-aryl-4-arylethynyl-1H-1,2,3- zoles with valuable photophysical and biological properties, using the synthetic approach triazoles with valuable photophysical and biological properties, using the synthetic ap- included CuAAC of azides to iodobuta‐1,3‐diynes and subsequent Suzuki‐Miyaura cross‐ proach included CuAAC of azides to iodobuta-1,3-diynes and subsequent Suzuki-Miyaura coupling. cross-coupling. 2.2. ResultsResults andand DiscussionDiscussion 2.1.2.1. SynthesisSynthesis andand StructuralStructural CharacterizationCharacterization ForFor thethe synthesissynthesis ofof startingstarting iodobuta-1,3-diynes,iodobuta‐1,3‐diynes, thethe four-stagefour‐stage syntheticsynthetic routeroute was was usedused (Scheme(Scheme1 1).). The The effectiveness effectiveness of of this this approach approach was was shown shown previously previously in in our our research research groupgroup [[35].35]. AtAt thethe firstfirst stage,stage, 2,7-dimethylocta-3,5-diyne-2,7-diol2,7‐dimethylocta‐3,5‐diyne‐2,7‐diol 11 waswas subjected to retro-retro‐ FavorskiiFavorskii reaction reaction by by the the heating heating with with K K22COCO33 [36,37][36,37] to synthesize 2 2-methylhexa-3,5-diyn-‐methylhexa‐3,5‐diyn‐ 2-ol2‐ol 2,2, whichwhich waswas subjectedsubjected toto Sonogashira Sonogashira coupling coupling with with iodoarenes iodoarenes3a 3a––cc[ 38[38].]. Obtained Obtained compoundscompounds 4a4a––cc werewere involvedinvolved inin retro-Favorskiiretro‐Favorskii reaction reaction again again using using KOH. KOH. Depending Depending onon thethe substituentssubstituents inin thethe arylaryl fragment,fragment, oneone ofof two methodologies ofof iodinationiodination waswas used:used: forfor electron-withdrawingelectron‐withdrawing substituted substituted acetylenes acetylenes5a 5aand and5b 5bNIS NIS in in the the presence presence AgNO AgNO33of of (i)(i) oror DBUDBU (ii) (ii) for for diacetylene diacetylene5c 5cwith with dimethylamino dimethylamino group. group. SchemeScheme 1. 1.Synthesis Synthesis of of iodobuta-1,3-diynes iodobuta‐1,3‐diynes6a 6a––cc.. ConvenientConvenient andand eco-friendlyeco‐friendly solvent-free solvent‐free methodology methodology using using CuI(PPh CuI(PPh33))33 inin thethe pres-pres‐ enceence ofof 2,6-lutidine2,6‐lutidine asas catalyticcatalytic systemsystem waswas usedused forfor thethe CuAACCuAAC reactionreaction ofof iodobuta-1,3-iodobuta‐1,3‐ diynesdiynes6a 6a––cc withwith methylmethyl 2-azidoacetate2‐azidoacetate7 7 [[39].39]. Recently, thethe efficiencyefficiency of of thisthis methodologymethodology forfor thethe synthesissynthesis ofof 4-ethynyl-5-iodo-1,2,3-triazoles4‐ethynyl‐5‐iodo‐1,2,3‐triazoles fromfrom iodobuta-1,3-diynes iodobuta‐1,3‐diynes was was shown shown Molecules 2021,, 26,, 2801x FOR PEER REVIEW 3 of 1415 by us [[35,40].35,40]. The choice of methyl 2 2-azidoacetate‐azidoacetate 7 as the dipolarophile caused by the potential ability ability of of derivatization derivatization of of the the ester ester group. group. It has It has been been shown shown that that cycloaddition cycloaddi- proceedstion proceeds strictly strictly regioselectively, regioselectively, giving giving only only5‐iodo 5-iodo-1,2,3-iodotriazoles‐1,2,3‐iodotriazoles (Scheme (Scheme 2). Ad2).‐ ductsAdducts 8a–8ac were–c were obtained obtained in good in good yields. yields. R CuI(PPh3)3, 8a: R = Cl, 71% OMe 2,6-lutidine 8b: R = CN, 87%, R I N3 + I 8c: R = NMe2, 69% O O N N OMe 6a c N 7 Scheme 2. Cycloaddition of azide 7 to iodobuta-1,3-diynesiodobuta‐1,3‐diynes 6a–c.
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