Heptafluorobutyric Acid-Induced Cross-Dehydrogenative Coupling Reactions of 1,2,4-Triazines. Part 2: p-Coupling with Arylamines

Heptafluorobutyric Acid-Induced Cross-Dehydrogenative Coupling Reactions of 1,2,4-Triazines. Part 2: p-Coupling with Arylamines | Authorea try { document.documentElement.classList.add('js'); } catch (e) { } var _gaq = _gaq || []; _gaq.push(['_setAccount', 'G-8VDV14Y67G']); _gaq.push(['_trackPageview']); (function() { var ga = document.createElement('script'); ga.type = 'text/javascript'; ga.async = true; ga.src = ('https:' == document.location.protocol ? 'https://ssl' : 'http://www') + '.google-analytics.com/ga.js'; var s = document.getElementsByTagName('script')[0]; s.parentNode.insertBefore(ga, s); })(); Skip to main content Preprints Collections Wiley Open Research IET Open Research Ecological Society of Japan All Collections About About Authorea FAQs Contact Us Quick Search anywhere Search for preprint articles, keywords, etc. Search Search ADVANCED SEARCH SCROLL This is a preprint and has not been peer reviewed. Data may be preliminary. 30 March 2026 V1 Latest version Share on Heptafluorobutyric Acid-Induced Cross-Dehydrogenative Coupling Reactions of 1,2,4-Triazines. Part 2: p-Coupling with Arylamines Authors : Anastasia P. Potapova , Elisaveta M. Gurina , Igor A. Khalymbadzha 0000-0002-8043-8023 , Anton N. Tsmokaluk , Ainur D. Sharapov , Vasiliy S. Gaviko , Dmitry S. Kopchuk , and Ramil F. Fatykhov [email protected] Authors Info & Affiliations https://doi.org/10.22541/au.177485101.19578299/v1 118 views 64 downloads Contents Abstract Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract Text：A heptafluorobutyric acid-induced cross-dehydrogenative coupling reaction of arylamines with 1,2,4-triazines has been described. This metal-free protocol enables regioselective para-C-H hetarylation of diverse arylamines including well-known fluorophore scaffolds, such as triphenylamine, carbazole and phenothiazine, with easily accessible 1,2,4-triazines under mild conditions. This approach has promise potential for drug development and material design. Cite this paper: Chin. J. Chem. 2025 , 43 , XXX—XXX. DOI: 10.1002/cjoc.70XXX Heptafluorobutyric Acid-Induced Cross-Dehydrogenative Coupling Reactions of 1,2,4-Triazines. Part 2: p -Coupling with Arylamines Anastasia P. Potapova, a Elisaveta M. Gurina, a Igor A. Khalymbadzha,* a,b Anton N. Tsmokaluk, a Ainur D. Sharapov, a Vasiliy S. Gaviko, a,c Dmitry S. Kopchuk, a and Ramil F. Fatykhov * a a Ural Federal University, 19 Mira Str., 620062 Ekaterinburg, Russia. b Research Center for Translational Medicine, Sirius University of Science and Technology, Olympic Ave. 1, 354340 Sochi, Russia c M.N. Mikheev Institute of Metal Physics of the Ural Branch of the Russian Academy of Sciences, 18 S. Kovalevskaya Str., 620108 Ekaterinburg, Russia Arylamine | 1,2,4-Triazine | Heptafluorobutyric Acid | Cross-Dehydrogenative Coupling | Nucleophilic Substitution of Hydrogen Comprehensive Summary Text：A heptafluorobutyric acid-induced cross-dehydrogenative coupling reaction of arylamines with 1,2,4-triazines has been described. This metal-free protocol enables regioselective para-C-H hetarylation of diverse arylamines including well-known fluorophore scaffolds, such as triphenylamine, carbazole and phenothiazine, with easily accessible 1,2,4-triazines under mild conditions. This approach has promise potential for drug development and material design. Background and Originality Content In recent years, the development of efficient and environmentally friendly processes for carbon-carbon bond formation that adhere to the principles of ”green chemistry” and the PASE (Pot, Atom and Step Economy) strategy has attracted much attention. The cross-dehydrogenative coupling (CDC) reactions most fully meet these requirements [1–3] and are intended to partially replace conventional C-X/C-Y cross-coupling (e.g., the transition metal-catalyzed Suzuki-Miyaura and the Stille reactions). The CDC strategy circumvents the pre-functionalization of starting substrates, shortening synthetic routes, enhancing efficiency and proving suitable for the late-stage functionalization of natural products and pharmaceuticals, [4–6] as well as for the synthesis of organic optoelectronic materials, [7,8] including nonlinear optics (NLO), organic light-emitting diodes (OLEDs) and solar cells. Figure 1 Selected examples of triazine-arylamines derivatives Electron-rich arylamines are privileged structural fragments, widely utilized as donor units in luminescence materials. [9–13] At the same time, electron-deficient aromatic azines, in particular, pyridine, [14] diazine [15,16] and 1,3,5-triazine, [17–19] serve as significant electron-withdrawing motifs in the design of push-pull azine-arylamine dyads for optoelectronic and optical materials. Most synthetic approaches to these dyads rely on Pd-catalyzed Suzuki-Miyaura coupling [20–23] or Buchwald–Hartwig amination [24,25] (Scheme 1a). Scheme 1 Approaches to azine-arylamine dyads Over the last decade, ambipolar organic molecules based on 1,2,4-triazine core as the strong electron acceptor have growing attention for a variety of optoelectronic applications. [26–28] In 2016, Lu et al. first reported a 1,2,4-triazine-phenoxazine triad (Fig. 1a) as a thermally activated delayed fluorescence (TADF) emitter for OLEDs. [29] Recently, Maggiore et al. demonstrated that condensed 1,2,4-triazines with a carbazole donor (Fig. 1b) simultaneously display TADF and room-temperature phosphorescence (RTP). [30] In 2020, Tang and co-workers designed a reddish-orange-emitting cationic iridium(III) complex containing a 1,2,4-triazine-carbazole bipolar unit (Fig. 1c) for neutral/warm white OLEDs. [31] Furthermore, the asymmetric triazine core has been used as a readily accessible and inexpensive building block for monoazine and diazine rings via the inverse electron-demand Diels–Alder (IEDDA) reactions. [32] Recently, our group developed a convenient protocol for the synthesis of 3-triazinyl-substituted coumarins via the heptafluorobutyric acid- (HFBA) induced CDC process between 7-(dialkylamino)coumarins and 1,2,4-triazines (Scheme 1b). [33] Inspired by this finding, we investigated whether the HFBA could activate triazine core for C-H/C-H cross-coupling with more aromatic rings such as arylamines including well-known fluorophore scaffolds, including triphenylamine, carbazole, and phenothiazine. Herein, we present the result of our investigation (Scheme 1c). Results and Discussion We began our study with the research of the N,N-dimethylaniline 1a as a coupling partner in the CDC reaction with 3-ethylthio-1,2,4-triazine 2a . Following our previously established protocol, [33] the desired product 3aa was obtained in high yield using 1.5 equiv. 2a and 50 mol % HFBA in AcOH at 80 °C (Table 1, Entry 1). However, 5,5′-bitriazine 2a′ was also isolated in 12% yield. Decreasing 1a : 2a ratio to 1:1.25 slightly increased yield of 3aa to 87% while suppressing the side reaction (Table 1, Entry 2). At the same time, using an equimolar ratio of substrates or decreased amount of HFBA has given worse results (Table 1, Entries 3 and 4). Other catalysts, such as trifluoroacetic acid (TFA), 3,3,3-trifluoropropionic acid or perfluoropentanoic acid (PFPeA), were less effective in the CDC reaction (Table 1, Entries 5-7). To our surprise, the reaction proceeded even in the absence of a catalyst, albeit with a poor yield (Table 1, Entry 8). Unfortunately, attempts to reduce the reaction time by using microwave irradiation led to increase yield of byproduct 2aa′ (Table 1, Entry 9). Therefore, the optimal conditions for the CDC reaction were determined to be 50 mol% HFBA at 80 °C for 8 h. Table 1 Optimization of reaction conditions a 1 ratio 1a : 2a is 1:1.5 82 19 2 none 87 5 3 ratio 1a:2a is 1:1 65 trace 4 25 mol % HFBA used 60 trace 5 TFA instead of HFBA 61 18 6 CF 3 CH 2 CO 2 H instead of HFBA 78 11 7 PFPeA instead of HFBA 58 21 8 without HFBA 29 0 9 microwave irradiation for 1h 59 31 a Reactions were carried out with 1a (0.2 mmol), 2a , HFBA in AcOH (1 ml) at 80 °C for 8 h. b Isolated yields. c ref. [33] With the optimized reaction conditions in hand, we next examined the substrate scope of the CDC protocol with respect to various anilines 1 (Fig. S1) and 1,2,4-triazines 2 (Fig. S2) and results are summarized in Scheme 2. We found that the anticipated CDC products 3aa - 3hc could be isolated in good yields for tertiary and secondary anilines ( 1a-d,g,h ). However, acetanilide 1e proved unreactive and only the starting materials were observed. Involving N,N-unsubstituted aniline 1f led to N-acetyl derivative 3ec in poor yield instead of 3fc . In this case, 1f likely undergoes competitive acetylation to form 1e , which is deactivated toward further coupling. Simultaneously, the product 3fc is acylated to form the isolated 3ec . Scheme 2 Scope of anilines 1 and triazines 2 Both electron-donating (ED) and electron-withdrawing (EW) groups at the ortho-position of the tertiary anilines ( 1i - l ) were tolerated, providing 3ia - la in moderate to good yields. Moreover, in the case of N,N-dimethyl-2-(pyrrolidin-1-yl)aniline 1j , the reaction occurred at the para-position relative to pyrrolidino-substituent with excellent regioselectivity and 52% yield, as confirmed by 2D NMR (HMBC and HSQC) experiments. A meta-methoxy group ( 1m ) did not affect efficiency of the process ( 3ma , 72%), whereas the bulky substituents like pyrrolidine ( 1n ) or phenyl ( 1o ) at the meta-position significantly decreased the yields (29-33%), likely due to steric hindrance. Surprisingly, an EW group at the meta-position ( 1p ) afforded desired 3pa , albeit in 21% yield. Even 2,3,5,6-tetrafluoroaniline 1q , which substantially has no nucleophilic properties (can be functionalized via primary C-H iodination, [34] C-H lithiation [35] or transition metal catalyzed C-H activation) [36,37] was successfully involved in the CDC reaction, yielding 3qa (15%). The use of para-substituted aniline 1r did not yield the corresponding ortho-coupling product 3ra . Annulated anilines 1s,t proved to be suitable substrates to give the desired products 3ra and 3sa in 51% and 71% yield, respectively. Furthermore, various partially hydrogenated N-heterocycles, such as tetrahydroquinolines 1u,v , 2,3-dihydro-1,4-benzothiazine 1w , indoline 1x and julolidine 1y , were also tolerated in this transformation, providing the corresponding para-substituted derivatives 3uc - 3yc in moderate to good yields. With the aniline substrate scope had studied, we next turned our attention to examine various (het)aryl-substituted triazines as coupling partner. When triazines bearing either electron-rich (4-methoxyphenyl ( 2d ) or thiophenyl ( 2e )) or electron-deficient (pyridinyl ( 2f ), pyrimidinyl ( 2g ) or pyrazinyl ( 2h )) (het)aryl substituents at the C3 position were employed, the corresponding CDC products 3 were obtained in moderate to high yields (Scheme 2). To our surprise, the CDC reaction between aniline 1c and previously unreported 3,3′-bi(1,2,4-triazine) 2i under standard conditions afforded only disubstituted derivative 3ci in a modest yield (21%). In contrast, the use of 3,6-disubstituted triazine 2j with aniline 1c unexpectedly led to 1,4-dihydrotriazine 3′cj in 92% yield, which was readily aromatized using a standard external oxidizing agent [38] to give 3cj in 93% yield. Inspired by these results, we next evaluated diphenylamines 4 (Fig. S1) in this CDC reaction (Scheme 3). It was found that diphenylamine 4a reacted smoothly with triazine 2a under standard reaction conditions to give mixture of mono- 5aa and di-triazinyl 6aa substituted derivatives in a ca. 1:2 ratio. In the case of triphenylamine 4b , mono-triazinyl derivative 5ba was produced in 54% yield as the major product. A small amount of di-substituted derivative 6ba was also isolated from the reaction mixture. Notably, no tri-substituted product was observed even with 3-fold excess of triazine was used. The use of triazine 3f in the reaction with 4b led to exclusively 5bf in a moderate yield. In contrast, the CDC reaction of 3,3′-bi(1,2,4-triazine) 2i with 4b afforded a mixture of mono- 5bi and bis- 5′bi functionalized bi(1,2,4-triazine) in 21% and 9% yield, respectively. Fused diphenylamines, such as carbazole 4c , acridan 4d , phenothiazine 4e and dibenzazepine 4f , were also tolerated, providing the corresponding mono-substituted products 5ca - 5fa in 21-55% yields. X-ray analysis of 5fa unambiguously established the structure and regioselectivity of the process. Scheme 3 Scope of diphenylamines 4 To demonstrate the synthetic potential of our protocol, several post-synthetic transformations were performed (Scheme 4). For instance, alkylthiotriazine derivative 3bc was subjected to the Liebeskind–Srogl cross-coupling with 4-(9 H -carbazol-9-yl)phenylboronic acid, followed by IEDDA reaction with 2,5-norbornadiene. [39] This sequence afforded pyridine 8 , providing access to functional materials. [40,41] Scheme 4 Representative modifications of the compounds 3 and 5 Photophysical studies have shown that compound 7 is characterized by ice blue or deep green fluoresce depending on used solvent (Table 2, Supplementary Figs. S4 and S5). Compounds 7 and 8 are the closest analogs of materials used in OLEDs. [41,42] On the other hand, the alkylation of 5ea with 3-dimethylaminopropyl chloride yielded an analogue of chlorpromazine and related phenothiazine antipsychotic drugs, [43] in good yield. It should be noted that neither chlorpromazine nor promazine themselves underwent the CDC with 1,2,4-triazine 2 under the standard conditions, highlighting the importance of the late-stage functionalization of the phenothiazine core prior to side-chain introduction. Table 2 Photophysical properties of compounds 7 and 8 in solutions (c = 10 -5 M) 7 (DCM) 237, 293, 342, 396 490 4844 (94) 3.7 2.02 7 (MeCN) 235, 291, 341, 392 517 6167 (125) 12.0 1.23 8 (DCM) 294, 328, 338sh 433 6491 (95) 24.1 9.94 8 (MeCN) 234, 292, 327, 338sh 433 8354 (133) 11.7 10.67 a Absorption spectra were measured at r.t. using Shimadzu UV-1800; b Emission spectra were measured at r.t. using Edinburgh FLS1000; c Absolute quantum yields were measured using the Integrating Sphere of the Edinburgh FLS1000 at r.t. Based on our experiments and previous reports, [44–46] we propose that the HFBA-induced CDC of arylamines with 1,2,4-triazines proceeds via a nucleophilic substitution of hydrogen (S N H ) mechanism (Scheme 5). In the initial step, protonation of triazine 2 by HFBA activates the ring toward nucleophilic attack. Subsequent addition of aniline 1 leads to the formation of the unstable dihydrotriazine A (so called σ H -adduct). In the case of reaction of triazine 2j with aniline 1c , the corresponding stable σ H -adduct 3′cj (see Supplementary Information) was isolated. This intermediate A undergoes a hydrogen atom transfer (HAT) to compound C providing the radical B . Similar radical was previously identified by EPR spectroscopy. [33] Radical B then eliminates an electron (SET) affording the desired CDC product 3 via deprotonation of D (Scheme 5). We were only able to register a weak signal of radical B in the EPR spectrum. [33] The low stability of B can be attributed to the shorter conjugation chain, in contrast to that previously described. [33] The proposed mechanism is supported by the fact that adding TEMPO to the starting materials accelerates the reaction by facilitating the abstraction of a hydrogen atom from A . Scheme 5 Plausible reaction pathway Conclusions We have developed a convenient and selective protocol for the HFBA-induced cross-dehydrogenative coupling of arylamines with 1,2,4-triazines. A diverse range of substrates, including anilines, partially hydrogenated N-heterocycles, and diphenylamines, underwent efficient para-C-H functionalization. This method affords the corresponding triazine-arylamine dyads with excellent regioselectivity and in yields of up to 87%. The developed protocol offers a metal-free, atom-economical strategy for the synthesis of complex molecular scaffolds with significant potential in materials science and medicinal chemistry. Experimental All commercially available chemicals were used without further purifications. Reactions were monitored by thin layer chromatography (TLC) carried out on silica gel Sorbfil TLC plates using UV light as visualizing agent. 1 H NMR and 13 C NMR spectra of all compounds except for 3qa were recorded on a Bruker DRX-400 Avance spectrometer ( 1 H, 400 MHz) in DMSO-d 6 or CDCl 3 as a solvent and an internal reference at ambient temperature. 1 H NMR and 13 C NMR spectra of 3qa were registered on a Bruker Avance NEO 600 spectrometer ( 1 H, 600 MHz) in CDCl 3 . Chemical shifts were reported in ppm and coupling constants are given in Hz. Data for 1 H NMR were recorded as follows: chemical shift (ppm), multiplicity (s, singlet; d, doublet; t, triplet; q, quartet; quin, quintet; sex, sextet; m, multiplet; br s, broad signal), coupling constant (Hz), integration. High resolution mass spectra were recorded on Agilent UHPLC/MS Accurate-Mass QTOF 1290/6545. Structural studies were performed using equipment available in the Collaborative Access Center “Testing Center of Nanotechnology and Advanced Materials” at the Mikheev Institute of Metal Physics, Ural Branch, Russian Academy of Sciences. The X-ray diffraction analysis was performed at room temperature on a Rigaku XtaLAB Synergy-S diffractometer. The calculations were performed using Olex 2 v. 171.41.120a 64-bit software. General procedures for the CDC reaction of arylamines with 1,2,4-triazines To a solution of arylamine 1 (0.4 mmol) and 1,2,4-triazine 2 (0.5 mmol) in acetic acid (1.5 ml), heptafluorobutyric acid (26 μl, 0.2 mmol) was added and the resulting mixture was heated at 80 °C for 8 h. The progress of the reaction was monitored by TLC. After completion of the reaction, the solvent was removed under reduced pressure. The residue was purified by column chromatography on silica gel using n-hexane/ethyl acetate as the eluent to afford the desired product. 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DOI: 10.1002/cjoc.70XXX Text for Table of Contents to summarize the article is required in 1‒3 lines. A metal-free heptafluorobutyric acid-induced cross-dehydrogenative coupling reaction of arylamines with 1,2,4-triazines has been described. This protocol enables regioselective para-C-H hetarylation of diverse arylamines, including triphenylamine, carbazole and phenothiazine, with easily accessible 1,2,4-triazines under mild conditions and high yields. Information & Authors Information Version history V1 Version 1 30 March 2026 Copyright This work is licensed under a Non Exclusive No Reuse License. Keywords 1 2 4-triazine arylamine cross-dehydrogenative coupling heptafluorobutyric acid nucleophilic substitution of hydrogen Authors Affiliations Anastasia P. Potapova Ural'skij federal'nyj universitet imeni pervogo Prezidenta Rossii B N El'cina View all articles by this author Elisaveta M. Gurina Ural'skij federal'nyj universitet imeni pervogo Prezidenta Rossii B N El'cina View all articles by this author Igor A. Khalymbadzha 0000-0002-8043-8023 Ural'skij federal'nyj universitet imeni pervogo Prezidenta Rossii B N El'cina View all articles by this author Anton N. Tsmokaluk Ural'skij federal'nyj universitet imeni pervogo Prezidenta Rossii B N El'cina View all articles by this author Ainur D. Sharapov Ural'skij federal'nyj universitet imeni pervogo Prezidenta Rossii B N El'cina View all articles by this author Vasiliy S. Gaviko Ural'skij federal'nyj universitet imeni pervogo Prezidenta Rossii B N El'cina View all articles by this author Dmitry S. Kopchuk Ural'skij federal'nyj universitet imeni pervogo Prezidenta Rossii B N El'cina View all articles by this author Ramil F. Fatykhov [email protected] Ural'skij federal'nyj universitet imeni pervogo Prezidenta Rossii B N El'cina View all articles by this author Metrics & Citations Metrics Article Usage 118 views 64 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation Anastasia P. Potapova, Elisaveta M. Gurina, Igor A. Khalymbadzha, et al. Heptafluorobutyric Acid-Induced Cross-Dehydrogenative Coupling Reactions of 1,2,4-Triazines. Part 2: p-Coupling with Arylamines. Authorea . 30 March 2026. DOI: https://doi.org/10.22541/au.177485101.19578299/v1 If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download. For more information or tips please see 'Downloading to a citation manager' in the Help menu . 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