Nd@g-C3N4 Dual-Functional Photocatalysis Enabled Fluoroalkylative Heteroarylation of Alkenes with RfSO2Cl as Both the Fuoroalkyl Radical and Chloride Radical Source

Nd@g-C3N4 Dual-Functional Photocatalysis Enabled Fluoroalkylative Heteroarylation of Alkenes with RfSO2Cl as Both the Fuoroalkyl Radical and Chloride Radical Source | 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 Search Search ADVANCED SEARCH SCROLL This is a preprint and has not been peer reviewed.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. 13 February 2025 V1 Latest version Share on Nd@g-C3N4 Dual-Functional Photocatalysis Enabled Fluoroalkylative Heteroarylation of Alkenes with RfSO2Cl as Both the Fuoroalkyl Radical and Chloride Radical Source Authors : Jia-Cheng Hou , Hai-Yang Song , Jun Jiang , Jia Peng , Hui Dai , Li-Fen Peng , Li-Juan Ou , and Wei-Min He 0000-0002-9481-6697 [email protected] Authors Info & Affiliations https://doi.org/10.22541/au.173943025.54799988/v1 210 views 129 downloads Contents Abstract Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract Semiconductor dual-functional photocatalysis composed of selective organic oxidation and reduction has attracted increasing a ttention owing to the green and environmental advantages. Herein, the Nd@g-C 3 N 4 dual-functional photocatalysis enabled fluoroalkylative heteroarylation of alkenes with R f SO 2 Cl under visible-light and ultrasound conditions was firstly reported. The photogenerated electron-driven reductive production of fluoroalkyl radical paired with photogenerated hole-driven oxidative production of chloride radical resulted in the full utilization of photogenerated carrier for bond formation. The use of sono-photocatalysis enhances both energy efficiency and the rate of chemical reactions. A wide range of N -heteroarenes, alkenes and R f SO 2 Cl, were well compatible for this reaction to access valuable fluoroalkylated N -heteroarenes with diverse structural features. We anticipate that this report will provide a sustainable synthetic protocol for fluoroalkylated N -heteroarenes but also develop the photoinduced chloride radical-mediated reaction and the dual-functional photocatalysis. Cite this paper: Chin. J. Chem. 2022 , 40 , XXX—XXX. DOI: 10.1002/cjoc.202200XXX Nd@g-C 3 N 4 Dual-Functional Photocatalysis Enabled Fluoroalkylative Heteroarylation of Alkenes with R f SO 2 Cl as Both the Fuoroalkyl Radical and Chloride Radical Source Jia-Cheng Hou a , Hai-Yang Song a , Jun Jiang a,d , Jia Peng a , Hui Dai a , Li-Fen Peng c , Li-Juan Ou b* , Wei-Min He a * a School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China b School of Materials Science and Engineering, Hunan Institute of Technology, Hengyang 421002, China c School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201, China, d National Engineering Research Center of Low-Carbon Processing and Utilization of Forest Biomass, Nanjing Forestry University, Nanjing 210037, China Semiconductor dual-functional photocatalysis composed of selective organic oxidation and reduction has attracted increasing a ttention owing to the green and environmental advantages. Herein, the Nd@g-C 3 N 4 dual-functional photocatalysis enabled fluoroalkylative heteroarylation of alkenes with R f SO 2 Cl under visible-light and ultrasound conditions was firstly reported. The photogenerated electron-driven reductive production of fluoroalkyl radical paired with photogenerated hole-driven oxidative production of chloride radical resulted in the full utilization of photogenerated carrier for bond formation. The use of sono-photocatalysis enhances both energy efficiency and the rate of chemical reactions. A wide range of N -heteroarenes, alkenes and R f SO 2 Cl, were well compatible for this reaction to access valuable fluoroalkylated N -heteroarenes with diverse structural features. We anticipate that this report will provide a sustainable synthetic protocol for fluoroalkylated N -heteroarenes but also develop the photoinduced chloride radical-mediated reaction and the dual-functional photocatalysis. Dual-functional photocatalysis | Dual role | Quinoxalin-2(1 H )-one | Fluoroalkylation | Fluoroalkyl sulfonyl chloride Background and Originality Content Heterogeneous photocatalysis with recyclable semiconductor photocatalyst is identified as an ideal organic synthetic method, which utilizes visible light to promote carbon-carbon/heteroatom bond formation under environmentally friendly and mild conditions. 1 However, sacrificial electron donor/acceptor reagents are widely applied for increasing the photogenerated carrier separation and migration efficiency by driving redox half reactions, resulting in rising environmental and economic cost as well as wasting the redox capacity of photogenerated carrier. The dual-functional photocatalysis composed of organic oxidation and reduction is considered as one of the most promising solutions to the limitation, because it can take full advantage of both photogenerated holes and electrons for producing value-added products. 2 Visible-light photoredox-catalyzed chloride radical (Cl˙)-mediated reaction has contributed significantly to the synthesis of value-added compounds during the past decades. 3 Although much progress has been made, most of these reactions rely on the usage of exogenous HCl/chloride salts as the Cl˙ source, which compromises the atom economy and increases the production cost. Fluoroalkyl sulfonyl chloride (R f SO 2 Cl) is a low cost and readily available fluoroalkylation reagent that has been widely used as the R f radical source for the visible-light photoinduced fluoroalkylation reaction. 4 In 2015, Zhang and Liu developed the UV-light photocatalyzed Cl˙-mediated trifluoromethylation with CF 3 SO 2 Cl as both the CF 3 radical and Cl˙ source via the homolysis of CF 3 SO 2 Cl under alkaline condition. 5 However, the use of harmful UV radiation (300 W Xe arclamp) restricts its practical application. The visible-light photo-oxidation of Cl anion into Cl˙ via single electron transfer (SET) is generally challenging, because the oxidation potential of Clˉ is much higher (E ox (Clˉ/Cl˙) = + 2.03 V vs. SCE in MeCN) 6 than the excited-state oxidation potentials of commonly used homogeneous photocatalysts. 7 To the best of our knowledge, visible-light photocatalyzed Cl˙-mediated fluoroalkylation reaction with R f SO 2 Cl as both the CF 3 radical and Cl˙ source remain elusive. Recently, our group developed the Ce@g-C 3 N 4 dual-functional photocatalysis of cooperative Cl˙-mediated alkylation of N ‑heteroarenes and hydrogen evolution with n Bu 4 NCl as the Cl˙ source. 8 Inspired by this work, we anticipate that semiconductor dual-functional photocatalysis can enable Cl-mediated fluoroalkylation with R f SO 2 Cl as both the CF 3 ˙ and Cl˙ source. Fluoroalkylated N -heterocycles are important N -heterocyclic derivatives encountered in numerous biologically active molecules, pharmaceuticals and organic materials. 9 Recently, the visible-light induced fluoroalkylative heteroarylation of alkenes with various fluoroalkylation reagents has emerged as a powerful tool for the homogeneous synthesis of fluoroalkylated N -heterocycles. 10 In 2023, Dolbier Jr reported the visible-light induced Ru(bpy) 3 Cl 2 ·6H 2 O-photocatalyzed fluoroalkylative heteroarylation of alkenes and R f SO 2 Cl with K 2 HPO 4 as the base additive (Scheme 1a). 11 Despite this success, the use of non-recyclable ruthenium-based photocatalyst and stoichiometric amounts of base additive eroded their overall appeal. Scheme 1 Visible-light Photoredox-Catalyzed Fluoroalkylative Heteroarylation of Alkenes with R f SO 2 Cl Sono-photocatalysis, which is characterized by the merits of combination of ultrasonic catalysis and photocatalysis, shows interesting advantages at the kinetic level and energy consumption. 12 However, sono-photocatalysis enabled organic bond formation reaction is extremely rare in the literature. 13 With our ongoing studies on photocatalysis, 14 herein, we wish to report the Nd@g-C 3 N 4 dual-functional photocatalysis enabled fluoroalkylative heteroarylation of alkenes with R f SO 2 Cl under visible light (or sunlight) and ultrasound irradiation conditions (Scheme 1b). R f SO 2 Cl acted as both the fuoroalkyl radical and Cl radical source, thus avoiding the usage of exogenous HCl/chloride salts. A broad range of fuoroalkylated N -heteroarenes could be obtained in good to excellent yields under base additive-, chemical redox regent- and sacrificial reagent-free conditions. Results and Discussion Table 1 Optimization of the reaction conditions a,b Entry Deviation from the above conditions Yield b 1 none 96 2 g-C 3 N 4 was used 41 3 Nd(NO 3 ) 3 was used N.R. 4 the mixture of g-C 3 N 4 and Nd(NO 3 ) 3 was used 43 5 K@g-C 3 N 4 was used 40 6 Fe@g-C 3 N 4 was used 49 7 Cu@g-C 3 N 4 was used 53 8 Zn@g-C 3 N 4 was used 37 9 Ag@g-C 3 N 4 was used 32 10 Ce@g-C 3 N 4 was used 80 11 fac -Ir(ppy) 3 , Ru(bpy) 3 Cl 2˙ 6H 2 O was used 21, 28 12 Rhodamine B, 4CzIPN was used 42, 35 13 Without a photocatalyst 19 14 Sunlight (30 h) was used 84 15 Stirring (24 h) was used 85 16 Air instead of N 2 N.R. 17 Without light N.R. a Conditions: 1a (0.2 mmol), 2a (0.3 mmol), 3a (0.3 mmol), catalyst (5 mg or 5 mol%), EtOH (2 mL), N 2 , Blue LED (7 W), US (22 kHz/30 W), r.t., 4 h. b Estimated by GC using dodecane as an internal reference. To explore the appropriate reaction conditions, 1-methylquinoxalin-2(1 H )-one ( 1a ), styrene ( 2a ) and CF 3 SO 2 Cl ( 3a ) were treated with the association of 7 W blue LED with Nd@g-C 3 N 4 as the heterogeneous photocatalyst and 22 kHz/30 W US for 4 h in EtOH under nitrogen atmosphere at room temperature. To our delight, the desired product 4aaa was generated in 96% GC yield (entry 1). In contrast, the intrinsic g-C 3 N 4 produced 4aaa in 41% GC yield and the single Nd(NO 3 ) 3 showed no reactivity in this reaction while no better performance was observed with mixing the g-C 3 N 4 and Nd(NO 3 ) 3 physically (entries 2 - 4). These results suggested that the catalytic activity of the composite photocatalyst were tremendously improved by dropping the Nd into intrinsic g-C 3 N 4. Replacing Nd with K, Fe, Cu, Zn, Ag or Ce in the composite photocatalyst led to a lower yield (entries 5 - 10). Compared to Nd@g-C 3 N 4, yields of 21% -42% were obtained with homogeneous noble metal photocatalysts [( fac -Ir(pp y) 3 and Ru(bpy) 3 Cl 2 ˙ 6H 2 O] and organic photocatalysts (Rhodamine B and 4CzIPN) (entries 11-12). The product 4aaa was obtained only in 19% yield without photocatalyst (entry 13). Using sunlight instead of blue light led to the formation of 4aaa in 84% yield (entry 14). Carrying out this reaction with conventional stirring for 24 hours delivered 4aaa in 85% yield (entry 15). No reaction occurred under the air atmosphere, suggesting that the presence of oxygen molecule suppressed this transformation (entry 16). Performing the template reaction in darkness gave no product (entry 17). Table 2 Reaction Scope a, b a Conditions: 1 (0.2 mmol), 2 (0.3 mmol), 3a (0.3 mmol), Nd@g-C 3 N 4 (5 mg), EtOH (2 mL), N 2 , Blue LED (7 W), US (22 kHz/30 W), r.t. b Isolated yields. Having established the optimum reaction conditions, we began to probe the generalizability of this reaction (Table 2). Firstly, quinoxalin-2(1 H )-ones bearing a series of aliphatic groups at N -position such as methyl, ethyl, n -pentyl, cyclopropylmethyl, ester, cyano, benzyloxycarbonyl (Cbz), benzyl (Bn), p -methoxybenzyl (PMB) reacted efficiently in this system to furnish the target products 4aaa - 4kaa in high yields and excellent regioselectivity. Notably, easily oxidizable allyl or propargyl group could survive in the reaction. To our delight, unprotected quinoxalin-2(1 H )-one was also well tolerated under standard conditions, yielding the product 4laa in 86%. Next, electron-donating (OMe) or electron-withdrawing groups (F, Cl, Br, CF 3 or NO 2 ) at the phenyl part of the substrates 1 had no effect on the reaction efficiencies and the desired products 4maa - 4saa were obtained in good yields. Di-substituted (Me or Cl) quinoxalin-2(1 H )-ones underwent this transformation well to afford the corresponding products 4taa and 4uaa in 90% and 84%, respectively. Pleasingly, a range of N -heteroarenes, including 1-methylbenzo[ g ]quinoxalin-2(1 H )-one, quinoxaline, 1-methyl-1,2-dihydroquinoxaline, quinazoline were suitable substrates and generated the desired products 4vaa - 4yaa in moderate to good yields. Table 3 Reaction Scope a, b a Conditions: 1a (0.2 mmol), 2 (0.3 mmol), 3 (0.3 mmol), Nd@g-C 3 N 4 (5 mg), EtOH (2 mL), N 2 , Blue LED (7 W), US (22 kHz/30 W), r.t. b Isolated yields. Next, the substrate scope with respect to alkenes ( 2 ) was examined (Table 3). The methyl group at C2 or C3-position of styrenes could participate well in this reaction to provide the desired products 4aba and 4aca in 85% and 81% isolated yields, respectively. Styrenes modified with electron-neutral (Ph), electron-donating (Me or t Bu) or electron-withdrawing groups (F, Cl, Br, CF 3 , Ac or CN) were well-compatible in the present transformation, affording the target compounds 4ada - 4ala in good yields. These results indicated that neither steric hindrance nor electronic effect of styrenes significantly influence the reaction efficiency. Moreover, 2-vinylnaphthalene also proceeded smoothly to give the product 4ama in 88% yield. Subsequently, various aliphatic alkenes were explored. It was gratifying to find that a variety of alkenes, including acyclic terminal ones (3-methylbutene, allylbenzene, ethyl acrylate and 2-phenylpropylene), acyclic internal ones (1-phenylpropylene and ethyl cinnamate) and cyclic ones (cyclohexene and norbornene) could deliver the corresponding products 4ana - 4ara in high yields. Gratifyingly, the reaction with phenylethyne gave product 4ava in good yield. To further investigate the reaction scope, various fluoroalkylation reagents were investigated. Both CHF 2 SO 2 Cl and perfluoroalkylsulfonyl chlorides (C 4 F 9 SO 2 Cl and C 6 F 13 SO 2 Cl) were readily converted into their corresponding products 4aab - 4aad in good yields. Scheme 3 Large-scale synthesis of 4aaa Figure 1 (a) The Reusability of Nd@g-C 3 N 4; (b) XRD patterns of fresh Nd@g-C 3 N 4 and recycled Nd@g-C 3 N 4 To demonstrate the synthetic utility of the present reaction, both the gram-scale synthesis and photocatalyst cycling experiments were performed. As shown in Scheme 3, carrying out the scaled-up template reaction (5 mmol) gave 4aaa in 83% yield (1.37 g). To our delight, reducing almost quarter of the loading of Nd@g-C 3 N 4 also led to a good yield of 4aaa (Scheme 3). Afterwards, photocatalyst recycling experiments were conducted in five consecutive reaction-separation processes in which Nd@g-C 3 N 4 could be easily recovered from and reused for next use only via centrifugation without an obvious loss of catalytic activity (Figure 1a). The nearly indistinguishable X-ray diffraction suggested that the basic structure of the recovered photocatalysts remained unchanged before and after experiments (Figure 1b). Scheme 4 Control experiments. To elucidate reaction mechanism of the dual-functional photocatalytic reaction, a series of mechanistic studies were conducted. First, this photochemical reaction was markedly inhibited in the presence of radical scavenger (TEMPO and 1,1-diphenylethylene), and TEMPO-CF 3 adduct 5aa , diphenylethene-CF 3 5ab and diphenylethene-Cl 5ac adduct were detected by GC-MS (Scheme 3a-b), demonstrating that both the CF 3 radical and Cl radical intermediates might be involved in the catalytic cycle. With photogenerated hole scavenger Na 2 S or photogenerated electron scavenger CCl 4 as the additive, the heterogeneous bond formation was entirely suppressed, indicating that both h + and e - were necessary for this photocatalytic process (Scheme 3c-d). The addition of SET inhibitor CuCl 2 to the reaction mixture did not result in any reaction, suggesting a SET process was involved in this transformation (Scheme 3e). The turn-on/off blue-light experimental results suggested that the continuous light irradiation is indispensable for the reaction to proceed. This observation and the quantum yield ( Φ = 6.08%, see the ESI† for details) of this transformation ruled out the possibility of a radical chain process. Scheme 4 Proposed reaction mechanism A plausible reaction mechanism was proposed based on the above-mentioned experimental results and relevant reports 5, 10g, 11, 15 (Scheme 4). First, the irradiation of Nd@g-C 3 N 4 by blue LED generates eˉ in the conduction band (CB) and h + in the valence band (VB). The special shell structure of Nd 3+ with unfilled 4f electron orbitals can trap eˉ to form the reduction state Nd 2+ , which then reduces R f SO 2 Cl into R f radical via a heterogeneous SET along with the extrusion of Clˉ and SO 2 . Subsequently, the R f radical can be trapped by the anti-Markovnikov addition of alkene 2 to produce the alkyl radical IM1 , which attacked the C=N bond of quinoxalin-2(1 H )-one 1 to yield the N-center radical IM2 , followed by a 1,2-H shift process to provide the C-center radical IM3 . A heterogeneous SET process from the dissociative Clˉ to h + give the Cl˙, which then abstracts a hydrogen atom from IM3 to deliver the target product 4 . Conclusions In conclusion, we for the first time demonstrated the Nd@g-C 3 N 4 dual-functional photocatalysis enabled fluoroalkylative heteroarylation of alkenes with R f SO 2 Cl under visible-light and ultrasound irradiation conditions. The photogenerated electron-driven reduction of R f SO 2 Cl into fluoroalkyl radical paired with photogenerated hole-driven oxidation chloride anion into chloride radical led to the full utilization of photogenerated carriers for bond formation. The dropping Nd into intrinsic g-C 3 N 4 largely improved the photocatalytic performance of Nd@g-C 3 N 4 . A broad range of N -heteroarene, alkenes and R f SO 2 Cl were well compatible for this reaction to access valuable fluoroalkylated N -heteroarenes with diverse structural features. R f SO 2 Cl served as both the R f radical and Cl radical source, thus simplifying this reaction system. The Nd@g-C 3 N 4 was also validated in both gram-scale synthesis, sunlight-induced photocatalysis and catalyst cycling experiment. Importantly, this strategy does not require any exogenous Cl anion reagents, chemical redox reagents or sacrificial reagents, which can proceed efficiently under sustainable and mild reaction conditions. We anticipate that this report will provide an efficient and green synthetic protocol for fluoroalkylated N -heteroarenes but also develop the photoinduced Cl radical-mediated reaction and the dual-functional photocatalysis. Experimental The mixture of 4-amino coumarin 1 (1.0 equiv., 0.2 mmol), N-fluorobenzenesulfonimide (2.0 equiv., 0.40 mmol), and H 2 O (5.0 equiv., 1.0 mmol, about 1 drop) in dimethyl carbonate (2.0 mL) was open to the air and stirred at room temperature under the irradiation of 10 W LED (455 nm) for about 12 h. After completion of the reaction, the resulting mixture was extracted with CH 2 Cl 2 (5 mL × 3) and the organic phase was then removed under vacuum. The residue was purified by flash column chromatography using a mixture of petroleum ether and ethyl acetate as eluent (PE/EA = 6/1-3/1) to give the desired α,α-difluoro-β-ketoamide products 3 . Supporting Information The supporting information for this article is available on the WWW under https://doi.org/10.1002/cjoc.2021xxxxx. Acknowledgement We are grateful for financial support from University of South China and Postgraduate Scientific Research Innovation Project of Hunan Province (No. CX20230949). References ( 1) (a) Savateev, A.; Antonietti, M. Heterogeneous Organocatalysis for Photoredox Chemistry. ACS Catal. 2018 , 8 , 9790-9808; (b) Verma, S. K.; Verma, R.; Girish, Y. R.; Xue, F.; Yan, L.; Verma, S.; Singh, M.; Vaishnav, Y.; Shaik, A. B.; Bhandare, R. R.; Rakesh, K. P.; Sharath Kumar, K. S.; Rangappa, K. S. 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(The following will be filled in by the editorial staff) Manuscript received: XXXX, 2022 Manuscript revised: XXXX, 2022 Manuscript accepted: XXXX, 2022 Accepted manuscript online: XXXX, 2022 Version of record online: XXXX, 2022 After acceptance, please insert a group photo of the authors taken recently. Left to Right: Authors Names Entry for the Table of Contents Nd@g-C 3 N 4 Dual-Functional Photocatalysis Enabled Fluoroalkylative Heteroarylation of Alkenes with R f SO 2 Cl as Both the Fuoroalkyl Radical and Chloride Radical Source Jia-Cheng Hou a , Hai-Yang Song a , Jun Jiang a,d , Jia Peng a , Hui Dai a , Li-Fen Peng c , Li-Juan Ou b* , Wei-Min He a * Chin. J. Chem. 2022 , 40 , XXX—XXX. DOI: 10.1002/cjoc.202200XXX Information & Authors Information Version history V1 Version 1 13 February 2025 Copyright This work is licensed under a Non Exclusive No Reuse License. Keywords dual role dual-functional photocatalysis fluoroalkyl sulfonyl chloride fluoroalkylation quinoxalin-2(1h)-one Authors Affiliations Jia-Cheng Hou University of South China View all articles by this author Hai-Yang Song University of South China View all articles by this author Jun Jiang University of South China View all articles by this author Jia Peng University of South China View all articles by this author Hui Dai University of South China View all articles by this author Li-Fen Peng Hunan University of Science and Technology View all articles by this author Li-Juan Ou Hunan Institute of Technology View all articles by this author Wei-Min He 0000-0002-9481-6697 [email protected] University of South China View all articles by this author Metrics & Citations Metrics Article Usage 210 views 129 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation Jia-Cheng Hou, Hai-Yang Song, Jun Jiang, et al. Nd@g-C3N4 Dual-Functional Photocatalysis Enabled Fluoroalkylative Heteroarylation of Alkenes with RfSO2Cl as Both the Fuoroalkyl Radical and Chloride Radical Source. Authorea . 13 February 2025. DOI: https://doi.org/10.22541/au.173943025.54799988/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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