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Alkene Diversification through a Molecular Recasting Strategy Enabled by N-Heterocyclic Carbene and Photoredox Dual Catalysis
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Qing-Zhu Li1, Mei-Hao He1, 2, Peng-Tao Wang1, Dong-Yang Xiang1, Long-Hai Hong1, Rong Zeng1, Jun-Long Li1, *
Research. Vol 8 Article ID 1010
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Research. Vol 8 Article ID 1010
• Research Article •
Alkene Diversification through a Molecular Recasting Strategy Enabled by N-Heterocyclic Carbene and Photoredox Dual Catalysis
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Qing-Zhu Li1, Mei-Hao He1, 2, Peng-Tao Wang1, Dong-Yang Xiang1, Long-Hai Hong1, Rong Zeng1, Jun-Long Li1, *
Affiliations
  • 1Anti-infective Agent Creation Engineering Research Centre of Sichuan Province, Sichuan Industrial Institute of Antibiotics, School of Pharmacy, Chengdu University, Chengdu 610106, China.
  • 2Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry and Sichuan Province, and Sichuan Research Center for Drug Precision Industrial Technology, West China School of Pharmacy, Sichuan University, Chengdu 610041, China.
About Author:

† These authors contributed equally to this work.

Published: 2025-12-20 doi: 10.34133/research.1010
Outline
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Alkenes are fundamental structural motifs in organic synthesis, valued for their prevalence in natural products and their broad reactivity profile. While traditional de novo synthesis offers access to diverse alkene frameworks, strategies enabling the direct structural remodeling of alkenes offer more concise and efficient alternatives, yet remain underdeveloped. Herein, we present a molecular recasting strategy for alkene diversification, enabled by N-heterocyclic carbene/photoredox dual catalysis. The transformation involves a sequential dealkenylative acylation and realkenylation cascade, realizing precise and modular reassembly of a broad spectrum of alkenes under mild conditions. This approach demonstrates exceptional generality, accommodating up to trisubstituted alkenes, and supports interconversion among diverse alkene frameworks, as well as late-stage functionalization of complex bioactive molecules. Mechanistic investigations reveal a radical-mediated catalytic pathway and shed light on the synergy of photoredox and N-heterocyclic carbene dual catalysis. This work provides a conceptually different and synthetically valuable platform for alkene editing.

Qing-Zhu Li, Mei-Hao He, Peng-Tao Wang, Dong-Yang Xiang, Long-Hai Hong, Rong Zeng, Jun-Long Li. Alkene Diversification through a Molecular Recasting Strategy Enabled by N-Heterocyclic Carbene and Photoredox Dual Catalysis[J]. Research, 2025 , 8 (12) : 1010 - . DOI: 10.34133/research.1010
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Introduction
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Alkenes are among the most fundamental and synthetically valuable classes of compounds in organic chemistry [1]. Their diverse reactivity and well-established transformation pathways have made them indispensable feedstocks in the synthesis of a wide array of fine chemicals, functional materials, and pharmaceutical agents [2–8]. Beyond their role as versatile synthetic building blocks, alkenes are also widely embedded in biologically active natural products and therapeutic molecules. Indeed, alkene motifs are often essential to the bioactivity of various compounds, including antibiotics, anticancer drugs, and pheromones [9–11]. Given their structural and functional significance, the development of novel strategies for rapid construction and diversification of alkenes continues to be a major objective in synthetic chemistry.
In contrast to numerous strategies that focus on the de novo construction of alkene carbon–carbon double bonds [12–17], the direct modification of alkenes offers a more efficient approach to accessing new alkene analogs. This approach enables the rapid generation of structurally varied alkenes from readily available alkene starting materials, thereby substantially streamlining synthetic processes and improving overall efficiency. Notably, direct alkene-to-alkene transformations have been extensively explored, particularly for polarized alkenes. For instance, electron-rich alkenes can participate as nucleophiles in C(sp2)-H functionalization reactions [18–21], whereas electron-deficient alkenes are amenable to modification via Lewis base-catalyzed transformations, exemplified by the Baylis–Hillman reaction [22,23]. Furthermore, transition-metal-catalyzed strategies, including Heck-type reactions [24–27] and C(sp2)-H activation processes [28–30], have broadened the scope to encompass simple, electron-neutral alkenes. Complementarily, cross-coupling methodologies have enabled the replacement of C–X bonds on alkenes with diverse functional groups, providing powerful tools for alkene diversification [31–33]. However, despite these advances, selective modification of alkenyl carbon substituents—such as simple alkyl or aryl groups on alkenes—remains challenging, primarily due to the intrinsic difficulty associated with inert C–C bond cleavage. Traditional approaches are generally ineffective for this type of bond activation (Fig. 1A). To overcome this limitation, methods such as olefin–olefin [34–36] and olefin–carbonyl metathesis [37–41] have been developed, enabling structural remodeling through C–C double bond cleavage and recombination (Fig. 1B, i). In a complementary strategy, Kwon and co-workers [42–50] introduced an elegant method involving ozone-mediated oxidation followed by transition-metal-catalyzed hemolytic C–C bond cleavage, offering a new paradigm for alkene activation. More recently, this strategy has been adapted to olefin–olefin metathesis, although its application is primarily limited to the synthesis of alkenes bearing up to 3 substituents (Fig. 1B, ii) [51]. Inspired by these advances, we envisioned an alkene recasting strategy: a dealkenylative acylation to form ketone intermediates, followed by olefination to regenerate the carbon–carbon double bond. This approach enables the modular and programmable reconstruction of alkene structures through sequential bond cleavage and formation (Fig. 1B, iii).
Building on our ongoing interest in radical N-heterocyclic carbene (NHC) organocatalysis [52–64], we herein report an efficient molecular recasting strategy for alkene diversification. This approach employs NHC/photoredox dual catalysis [65,66] to achieve dealkenylative radical acylation, followed by realkenylation, thereby enabling modular diversification at up to 3 substituent sites. Furthermore, additional functionalization of the ketone intermediate provides the opportunity to modify all 4 substituent positions. This strategy exhibits excellent substrate scope and functional group tolerance and can be successfully applied to the late-stage modification of complex bioactive molecules. Moreover, mechanistic studies further illuminate the radical-based pathway and key features of the dual catalytic cycle (Fig. 1C).
Results and Discussion
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Optimization of the reaction conditions
To validate our proposed alkene recasting strategy, we initiated a proof-of-concept study involving the transformation of a methyl substituent into a phenyl ring on a simple alkene model substrate (1a). We first conducted extensive screening of reaction parameters for the dealkenylative acylation step (see Tables S1 to S5), and the optimized conditions are summarized in Fig. 2. In this process, alkene 1a was activated by tetrazine A, generating the pro-aromatic 1,4-dihydropyridazine intermediate 2a [67,68]. Subsequent C–C bond cleavage and radical acylation with acyl-transfer reagent 3a proceeded smoothly under the dual catalysis of a triazolium NHC (N1) and the photocatalyst 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN, PC1). Under these conditions, the desired ketone 4a was obtained in 81% overall yield in a one-pot manner (entry 1). In contrast, alternative triazolium NHC catalysts (N2 to N4) resulted in lower efficiencies (entries 2 to 4). Similarly, switching to the imidazolium-based NHC precursor N5 afforded a reduced yield of 68% (entry 5), while the thiazolium variant N6 proved entirely ineffective, delivering no detectable product (entry 6). Evaluation of alternative photocatalysts revealed that structural modifications to 4CzIPN (e.g., PC2 and PC3) failed to enhance the reaction outcome (entries 7 and 8), and the use of Ir(III)-based complexes (PC4 and PC5) resulted in slightly lower yields (entries 9 and 10). A solvent screen further confirmed that acetonitrile was optimal, as dichloromethane (DCM), dimethylformamide, tetrahydrofuran, and dimethyl sulfoxide all led to diminished efficiency (entries 11 to 14). As expected, the reaction did not proceed in the absence of either the NHC catalyst or photocatalyst (entry 15). Finally, the resulting ketone intermediate could be rapidly converted to alkene 5 in 90% yield using the Tebbe reagent, thereby enabling direct access to a phenyl-substituted olefin.
Scope of the reaction
With the optimized conditions established, we next undertook a systematic investigation of the generality and limitations of this alkene recasting strategy (Fig. 3). Given the impressive efficiency observed in the final alkenylation step, our investigation primarily focused on evaluating the performance of the preceding dealkenylative acylation. As illustrated in Fig. 3A, a broad array of aryl-substituted N-acylsuccinimides 3 bearing diverse electronic and steric profiles smoothly reacted with methyl alkene 1a, affording aryl ketones 5 to 18 in isolated yields ranging from 46% to 76%. The protocol was also effective with N-acylsuccinimides bearing a naphthyl group (19), as well as heteroaryl substituents such as thienyl and pyridinyl rings (20 and 21). Furthermore, both cyclic and linear alkyl-substituted N-acylsuccinimides engaged effectively in this transformation, delivering the corresponding products 22 to 25. We then turned to examine the reactivity of a variety of terminal alkenes (Fig. 3B). Benzyl-substituted alkenes bearing different aryl groups performed efficiently, likely due to the resonance stabilization of the resulting benzylic radicals (26 to 29). Notably, replacing the aryl group with an ether moiety as the radical-stabilizing unit (30) still enabled productive acylation. Remarkably, even unactivated terminal alkenes lacking stabilizing substituents were viable substrates. Despite a modest decrease in yields, these simple alkenes bearing primary, secondary, or tertiary alkyl groups (31 to 37) successfully underwent the dealkenylative acylation, underscoring the broad functional group tolerance and robustness of this strategy. To further highlight the synthetic utility and broad applicability of this strategy, we applied the optimized reaction conditions to the late-stage functionalization of structurally complex, bioactive molecules. As shown in Fig. 3C, the methyl group in model alkene 1a could be replaced with diverse pharmacophore-derived fragments. For example, substrates derived from probenecid (38) or linoleic acid (39) participated smoothly in the transformation. Moreover, the method proved amenable to structural elaboration of alkenes derived from ciprofibrate (40), ibuprofen (41), and ezetimibe (42), highlighting the compatibility of this protocol with medicinally relevant scaffolds and its potential in drug modification and analog development.
The synthetic utility of the alkene recasting strategy
The synthetic utility of this alkene recasting strategy was further demonstrated by employing alkene substrates bearing substituents beyond the simple methyl group. These alkenes successfully engaged in fragment exchange reactions with diverse acyl-transfer reagents, enabling a range of synthetically interesting transformations. As illustrated in Fig. 4A, an ethyl-substituted alkene was efficiently transformed into a phenyl-substituted alkene (43 → 33), while the terminal methyl group could be formally replaced with a phenyl fragment (25 → 24). Remarkably, the method also allowed the phenyl alkene to be converted into a cyclohexyl alkene (5 → 23), effectively mimicking a challenging chemoselective hydrogenation of an aromatic ring. Subsequently, we demonstrated that the aryl-to-aryl fragment exchange is also feasible, and we can thus realize the formal editing of aryl substituents on alkenes. For instance, we achieved the formal deletion of a methyl group (7 → 5), selective deuteration of aryl C(sp2)-H bonds (5 → 44), and diverse site-selective installation of functional groups on the aromatic ring (35 → 45 and 35 → 46). Next, we found that the ketone intermediate 4a, obtained through dealkenylative acylation, could be directly employed in the subsequent realkenylation step without prior purification. The one-pot protocol afforded product 5 in 61% overall yield, thereby enabling rapid alkene structural editing. This streamlined protocol was readily scalable and applicable to the late-stage functionalization of pharmaceuticals (Fig. 4B). The reaction with a mixture of different alkenes, including 1a, monosubstituted (47), 1,2-disubstituted alkenes (48), and trisubstituted alkenes (49), offered the same alkene product 5. This convergent reaction could also be conducted in a one-pot procedure, delivering 5 in 50% overall yield (Fig. 4C).
In addition, as depicted in Fig. 4D, we explored the multi-site diversification of alkene 1a to showcase the full potential of this alkene recasting strategy. Using malononitrile as the alkenylation reagent, the terminal alkenyl C–H bonds were successfully modified, affording a tetrasubstituted alkene (50). Notably, by introducing an additional transformation at the α-position of ketone intermediate 4a prior to alkenylation, it was possible to install up to 4 distinct substituents on the alkene framework (51 to 53), highlighting the modularity and synthetic flexibility of this approach (for additional examples of alkene diversification on multiple sites, see the Supplementary Materials).
Mechanistic investigations and the proposed mechanism
To better elucidate the underlying mechanism of the key dealkenylative acylation step, we conducted a series of mechanistic studies, as outlined in Fig. 5A. We began by isolating intermediate 2a, derived from the alkene substrate, and subjected it to the standard catalytic conditions in the presence of the radical scavenger 2,2,6,6-tetramethyl-piperidinyloxy (TEMPO). Under these conditions, ketone formation was completely suppressed, and the TEMPO-trapped adduct 54 was obtained, providing compelling evidence for a radical-based process (Fig. 5A, i). Further support came from a radical clock experiment employing a cyclopropyl-substituted substrate 2b, which underwent ring opening to give product 55 in 31% yield, consistent with radical intermediacy (Fig. 5A, ii).
Next, to assess the role of the NHC-derived acyl azolium species, we replaced both the NHC precursor and 3a with a pre-synthesized acyl azolium 56. Gratifyingly, this surrogate also furnished the ketone product 4a under otherwise identical conditions, indicating that the acyl azolium intermediate is catalytically competent and likely plays a central role in the dual catalytic cycle (Fig. 5A, iii). Then, we turned our attention to the photoredox catalytic process. Quantum yield measurement gave a value of Φ = 0.685, suggesting a photocatalytic rather than a chain-propagated mechanism (Fig. 5A, iv). This conclusion was further corroborated by a light on/off experiment, in which product 4a was formed only during irradiation periods (Fig. 5A, v). Ultraviolet–visible absorption analysis revealed that only the photocatalyst 4CzIPN exhibited remarkable absorption in the visible region, while the substrates, NHC catalysts, and acyl azolium intermediates did not display marked absorption individually or in combination (Fig. 5A, vi). Furthermore, Stern–Volmer luminescence quenching experiments demonstrated that the excited state of 4CzIPN is selectively quenched by acyl azolium 56, but not by 2a (Fig. 5A, vii). These results point toward a single-electron transfer event from the excited photocatalyst 4CzIPN* (E1/2PC+·/PC* = −1.18 V vs. saturated calomel electrode [SCE]) [69] to the acyl azolium species acyl azolium 56 (Ered = −1.13 V vs. SCE) [70]. The subsequent oxidation of the intermediate 2 (Eox = +1.42 V vs. SCE) [67,68] by 4CzIPN+· (E1/2PC+·/PC = +1.49 V vs. SCE) [69], given its favorable redox potential, is also thermodynamically feasible.
Drawing from the experimental findings, we propose a mechanistic pathway for this alkene recasting protocol, as depicted in Fig. 5B. The cycle is initiated by the formation of acyl azolium intermediate I via NHC organocatalysis. Upon photoexcitation, the photocatalyst 4CzIPN reaches its excited state (4CzIPN*), which then undergoes a single-electron transfer with the acyl azolium to generate the ketyl radical species II alongside the oxidized photocatalyst 4CzIPN+·. Concurrently, the in situ formed dihydropyridazine intermediate 2, originating from the alkene substrate 1, donates an electron to 4CzIPN+·, thereby restoring the ground-state photocatalyst and generating radical species III. A subsequent deprotonation of III leads to the formation of the nitrogen-centered radical IV, which undergoes fragmentation to yield the carbon-centered radical V. These 2 radical species then engage in a radical–radical cross-coupling event, constructing the key C–C bond while simultaneously releasing the NHC catalyst to furnish the ketone intermediate 4. This ketone is then subjected to an olefination process, completing the rapid transformation and delivering the final alkenylated product. Through this sequence, a formal editing of the alkene framework is accomplished with high structural precision.
In conclusion, we have developed a modular alkene recasting strategy based on a dealkenylative acylation and realkenylation cascade, enabled by NHC/photoredox dual catalysis. This protocol allows for efficient and selective diversification of alkenes, providing access to structurally diverse derivatives from a broad range of alkene substrates. The present approach demonstrates high functional group tolerance and broad applicability, including the late-stage modification of pharmaceutically relevant molecules. Mechanistic studies support the proposed dual catalytic cycle and underscore the role of radical intermediates in driving the transformation. This work expands the toolbox for NHC-catalyzed molecular editing, and further developments along this line are currently in progress.
Materials and Methods
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General information
Commercial reagents and solvents were obtained from Adamas-beta, Aldrich Chemical Co., Alfa Aesar, Macklin, Energy Chemical, and Leyan. Analytical thin-layer chromatography was performed on silica gel HSGF254 glass plates (purchased from Jiangyou Silica Gel Development Co., Ltd, Yantai, China) containing a 254-nm fluorescent indicator. Flash column chromatography was performed over silica gel (40 to 45 μm, 300 to 400 mesh). 1H nuclear magnetic resonance (NMR) and 13C NMR spectra were recorded at 25 °C on a JEOL JNM-ECZ600R/S1 spectrometer. High-resolution mass spectrometry was performed on an Agilent 6230 time-of-flight liquid chromatography/mass spectrometry instrument or a Waters SYNAPT G2 mass spectrometer by using an electrospray ionization source analyzed by quadrupole time-of-flight mass spectrometry. Melting points were determined on a SGW X-4 digital melting point apparatus, and temperatures were not corrected.
Procedure for “one-pot” diversification
A dry glass tube was charged with alkene 1a (0.1 mmol), tetrazine A (0.11 mmol), and DCM (2 ml). Then, the resulting mixture was stirred for 7 h at room temperature. After the reaction finished, the reaction mixture was concentrated in vacuum to give the crude intermediate 2a, and then N-acylsuccinimide 3a (0.2 mmol), NHC N1 (0.02 mmol), PC1 (0.002 mmol), and K2CO3 (0.2 mmol) were added. The reaction tube was subjected to 3 cycles of pressurization and depressurization using dry Ar. Afterward, 1 ml of methyl cyanide was added, and the reaction mixture was stirred for 8 h under the irradiation of blue light-emitting diodes. Then, the mixture was concentrated in vacuum. Subsequently, the glass tube was subjected to 3 cycles of pressurization and depressurization using dry Ar. Under the protection of an Ar atmosphere, toluene (1 ml), the Tebbe reagent (0.3 mmol) and pyridine (0.3 mmol) were successively added. The reaction was stirred for 5 h at 40 °C. Then, the reaction mixture was diluted with water and extracted with DCM. The combined organic phases were washed with brine, dried over anhydrous Na2SO4, filtered, and concentrated in vacuum. The crude residue was then purified by column chromatography on silica gel eluting with petroleum ether/ethyl acetate to provide the alkene product 5.
Funding
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  • National Natural Science Foundation of China(22271028)
  • National Natural Science Foundation of China(22071011)
  • National Natural Science Foundation of China(22203010)
  • National Natural Science Foundation of China(22301023)
  • Department of Science and Technology of Sichuan Province(2023NSFSC2001)
  • Department of Science and Technology of Sichuan Province(2024NSFTD0023)
  • Special Project for Research and Development in Key areas of Guangdong Province(2022B1111050003)
References
Less
1.
Patai S, editor. The chemistry of alkenes. London (England): Wiley; 1964.
2.
Dong Z, Ren Z, Thompson SJ, Xu Y, Dong G. Transition-metal-catalyzed C–H alkylation using alkenes. Chem Rev. 2017;117(13):9333–9403.
3.
Jiang H, Studer A. Intermolecular radical carboamination of alkenes. Chem Soc Rev. 2020;49(6):1790–1811.
4.
Tang S, Nozaki K. Advances in the synthesis of copolymers from carbon dioxide, dienes, and olefins. Acc Chem Res. 2022;55(11):1524–1532.
5.
Kohlhepp SV, Gulder T. Hypervalent iodine(III) fluorinations of alkenes and diazo compounds: New opportunities in fluorination chemistry. Chem Soc Rev. 2016;45(22):6270–6288.
6.
Molloy JJ, Morack T, Gilmour R. Positional and geometrical isomerisation of alkenes: The pinnacle of atom economy. Angew Chem Int Ed. 2019;58(39):13654–13664.
7.
Zeng H, Yin R, Zhao Y, Ma J-A, Wu J. Modular alkene synthesis from carboxylic acids, alcohols and alkanes via integrated photocatalysis. Nat Chem. 2024;16(11):1822–1830.
8.
Tang S, Liu K, Liu C, Lei A. Olefinic C–H functionalization through radical alkenylation. Chem Soc Rev. 2015;44(5):1070–1082.
9.
Davidson MH, Johnson J, Rooney MW, Kyle ML, Kling DF. A novel omega-3 free fatty acid formulation has dramatically improved bioavailability during a low-fat diet compared with omega-3-acid ethyl esters: The ECLIPSE (Epanova® compared to Lovaza® in a pharmacokinetic single-dose evaluation) study. J Clin Lipidol. 2012;6(6):573–584.
10.
Orvis AK, Wesson SK, Breza TS, Church AA, Mitchell CL, Watkins SW. Mycophenolate mofetil in dermatology. J Am Acad Dermatol. 2009;60(2):183–199.
11.
Zharkawi MMZ, Farid NF, Hassan MH, Hassan SA. New chemometrics-assisted spectrophotometric methods for simultaneous determination of co-formulated drugs montelukast, rupatadine, and desloratadine in their different dosage combinations. BMC Chem. 2024;18(1):232.
12.
Cuenca AB, Fernández E. Boron-Wittig olefination with gem-bis(boryl)alkanes. Chem Soc Rev. 2021;50(1):72–86.
13.
Roman D, Sauer M, Beemelmanns C. Applications of the Horner–Wadsworth–Emmons olefination in modern natural product synthesis. Synthesis. 2021;53(16):2713–2739.
14.
Janicki I, Kiełbasiński P. Still–Gennari olefination and its applications in organic synthesis. Adv Synth Catal. 2020;362(13):2552–2596.
15.
Rinu PXT, Radhika S, Anilkumar G. Recent applications and trends in the Julia-Kocienski olefination. Chem Sel. 2022;7(31):Article e202200760.
16.
Li X, Song Q. Recent progress on the Zweifel olefination: An update. Synthesis. 2024;56(13):1979–1988.
17.
Aubele DL, Wan S, Floreancig PE. Total synthesis of (+)-dactylolide through an efficient sequential Peterson olefination and Prins cyclization reaction. Angew Chem Int Ed. 2005;44(22):3485–3488.
18.
Li Y, Cheng K, Lu X, Sun J. A facile and efficient approach to N-protected-β-sulfinyl-enamines via C-sulfinylation of enamides and enecarbamates. Adv Synth Catal. 2010;352(11–12):1876–1880.
19.
Guarda EA, Marzari MRB, Frizzo CP, Guarda PM, Zanatta N, Bonacorso HG, Martins MAP. Enol ethers and acetals: Acylation with dichloroacetyl, acetyl and benzoyl chloride in ionic liquid medium. Tetrahedron Lett. 2012;53(2):170–172.
20.
Wu P, Lin D, Lu X, Zhou L, Sun J. Trimethylchlorosilane-promoted aza-Mannich reaction of enecarbamates and aldimines. Tetrahedron Lett. 2009;50(52):7249–7251.
21.
Prakash M, Muthusamy S, Kesavan V. Copper(I) bromide catalyzed arylation of cyclic enamides and naphthyl-1-acetamides using diaryliodonium salts. J Org Chem. 2014;79(17):7836–7843.
22.
Basavalah D, Reddy BS, Badsara SS. Recent contributions from the Baylis–Hillman reaction to organic chemistry. Chem Rev. 2010;110(9):5447–5674.
23.
Wei Y, Shi M. Recent advances in organocatalytic asymmetric Morita–Baylis–Hillman/aza-Morita–Baylis–Hillman reactions. Chem Rev. 2013;113(8):6659–6690.
24.
Heck RF, Nolley JP. Palladium-catalyzed vinylic hydrogen substitution reactions with aryl, benzyl, and styryl halides. J Org Chem. 1972;37(14):2320–2322.
25.
Heck RF. Palladium-catalyzed reactions of organic halides with olefins. Acc Chem Res. 1979;12(4):146–151.
26.
Oestreich M, editor. The Mizoroki−Heck reaction. Chichester (England): Wiley; 2009.
27.
Bräse S, De Meijere A. Cross-coupling of organyl halides with alkenes: The Heck reaction. In: De Meijere A, Diederich F, editors. Metal-catalyzed cross-coupling reactions. Weinheim (Germany): Wiley-VCH; 2004. p. 217–315.
28.
Wang K, Hu F, Zhang Y, Wang J. Directing group-assisted transition-metal-catalyzed vinylic C–H bond functionalization. Sci China Chem. 2015;58(8):1252–1265.
29.
Maraswami M, Loh T-P. Transition-metal-catalyzed alkenyl sp2 C–H activation: A short account. Synthesis. 2019;51(05):1049–1062.
30.
Wang Y, Zhu Y, Xu L, He R, Zhang J. Recent advances in geminal-group-directed alkenyl C–H functionalization. Chin J Org Chem. 2022;42(7):2000–2014.
31.
Pang X, Peng X, Shu X-Z. Reductive cross-coupling of vinyl electrophiles. Synthesis. 2020;52(24):3751–3763.
32.
Lu M-Z, Goh J, Maraswami M, Jia Z, Tian J-S, Loh T-P. Recent advances in alkenyl sp2 C–H and C–F bond functionalizations: Scope, mechanism, and applications. Chem Rev. 2022;122(24):17479–17646.
33.
Feng Y-L, Zhang B-W, Xu Y, Jin S, Mazzarella D, Cao Z-Y. The reactivity of alkenyl boron reagents in catalytic reactions: Recent advances and perspectives. Org Chem Front. 2024;11(24):7249–7277.
34.
Ogba OM, Warner NC, O’Leary DJ, Grubbs RH. Recent advances in ruthenium-based olefin metathesis. Chem Soc Rev. 2018;47(12):4510–4544.
35.
Hoveyda AH, Qin C, Sui XZ, Liu Q, Li X, Nikbakht A. Taking olefin metathesis to the limit: Stereocontrolled synthesis of trisubstituted alkenes. Acc Chem Res. 2023;56(18):2426–2446.
36.
Montgomery TP, Ahmed TS, Grubbs RH. Stereoretentive olefin metathesis: An avenue to kinetic selectivity. Angew Chem Int Ed. 2017;56(37):11024–11036.
37.
Albright H, Davis AJ, Gomez-Lopez JL, Vonesh HL, Quach PK, Lambert TH, Schindler CS. Carbonyl–olefin metathesis. Chem Rev. 2021;121(15):9359–9406.
38.
Becker MR, Watson RB, Schindler CS. Beyond olefins: New metathesis directions for synthesis. Chem Soc Rev. 2018;47(21):7867–7881.
39.
Ravindar L, Lekkala R, Rakesh KP, Asiri AM, Marwani HM, Qin H-L. Carbonyl–olefin metathesis: A key review. Org Chem Front. 2018;5(8):1381–1391.
40.
Ludwig JR, Zimmerman PM, Gianino JB, Schindler CS. Iron(III)-catalysed carbonyl–olefin metathesis. Nature. 2016;533(7603):374–379.
41.
Ma L, Li W, Xi H, Bai X, Ma E, Yan X, Li Z. FeCl3-catalyzed ring-closing carbonyl–olefin metathesis. Angew Chem Int Ed. 2016;55(35):10410–10413.
42.
Šimek M, Dworkin JH, Kwon O. Synthesis through C(sp3)–C(sp2) bond scission in alkenes and ketones. Acc Chem Res. 2025;58(9):1547–1561.
43.
Smaligo AJ, Swain M, Quintana JC, Tan MF, Kim DA, Kwon O. Hydrodealkenylative C(sp3)–C(sp2) bond fragmentation. Science. 2019;364(6441):681–685.
44.
He Z, Moreno JA, Swain M, Wu J, Kwon O. Aminodealkenylation: Ozonolysis and copper catalysis convert C(sp3)–C(sp2) bonds to C(sp3)–N bonds. Science. 2023;381(6660):877–886.
45.
Smaligo AJ, Kwon O. Dealkenylative thiylation of C(sp3)–C(sp2) bonds. Org Lett. 2019;21(21):8592–8597.
46.
Smaligo AJ, Wu J, Burton NR, Hacker AS, Shaikh AC, Quintana JC, Wang R, Xie C, Kwon O. Oxodealkenylative cleavage of alkene C(sp3)–C(sp2) bonds: A practical method for introducing carbonyls into chiral pool materials. Angew Chem Int Ed. 2020;59(3):1211–1215.
47.
Swain M, Bunnell TB, Kim J, Kwon O. Dealkenylative alkynylation using catalytic FeII and vitamin C. J Am Chem Soc. 2022;144(32):14828–14837.
48.
Dehnert BW, Dworkin JH, Kwon O. Dealkenylative functionalizations: Conversion of alkene C(sp3)–C(sp2) bonds into C(sp3)–X bonds via redox-based radical processes. Synthesis. 2024;56(01):71–86.
49.
Dehnert BW, Yin Y, Kwon O. Halodealkenylation: Ozonolysis and catalytic FeII with vitamin C convert C(sp3)–C(sp2) bonds to C(sp3)–halide bonds. Org Lett. 2024;26(50):10921–10927.
50.
Dworkin JH, Chen ZM, Cheasty KC, Rubio AV, Kwon O. Hydrodealkenylative C(sp3)–C(sp2) bond fragmentation using Isayama–Mukaiyama peroxidation. J Am Chem Soc. 2025;147(16):13531–13544.
51.
Swain M, Sadykhov G, Wang R, Kwon O. Dealkenylative alkenylation: Formal σ-bond metathesis of olefins. Angew Chem Int Ed. 2020;59(40):17565–17571.
52.
Liu K, Schwenzer M, Studer A. Radical NHC catalysis. ACS Catal. 2022;12(19):11984–11999.
53.
Ishii T, Nagao K, Ohmiya H. Recent advances in N-heterocyclic carbene-based radical catalysis. Chem Sci. 2020;11(22):5630–5636.
54.
Li Q-Z, Zeng R, Han B, Li J-L. Single-electron transfer reactions enabled by N-heterocyclic carbene organocatalysis. Chem Eur J. 2021;27(10):3238–3250.
55.
Li Q-Z, Kou X-X, Qi T, Li J-L. Merging N-heterocyclic carbene organocatalysis with hydrogen atom transfer strategy. ChemCatChem. 2023;15(4):Article e202201320.
56.
Cai H, Yang X, Ren S-C, Chi YR. Radical reactions with N-heterocyclic carbene (NHC)-derived acyl azoliums for access to multifunctionalized ketones. ACS Catal. 2024;14(11):8270–8293.
57.
Li J-L, Liu Y-Q, Zou W-L, Zeng R, Zhang X, Liu Y, Han B, He Y, Leng H-J, Li Q-Z. Radical acylfluoroalkylation of olefins through N-heterocyclic carbene organocatalysis. Angew Chem Int Ed. 2020;59(5):1863–1870.
58.
Li Q-Z, Zeng R, Fan Y, Liu Y-Q, Qi T, Zhang X, Li J-L. Remote C(sp3)–H acylation of amides and cascade cyclization via N-heterocyclic carbene organocatalysis. Angew Chem Int Ed. 2022;61(15):Article e202116629.
59.
Li Q-Z, Liu Y-Q, Kou X-X, Zou W-L, Qi T, Xiang P, Xing J-D, Zhang X, Li J-L. Oxidative radical NHC catalysis: Divergent difunctionalization of olefins through intermolecular hydrogen atom transfer. Angew Chem Int Ed. 2022;61(44):Article e202207824.
60.
Li Q-Z, Zeng R, Xu P-S, Jin X-H, Xie C, Yang Q-C, Zhang X, Li J-L. Direct acylation of unactivated alkyl halides with aldehydes through N-heterocyclic carbene organocatalysis. Angew Chem Int Ed. 2023;62(40):Article e202309572.
61.
Huang H, Yu Z-Y, Han L-Y, Wu Y-Q, Jiang L, Li Q-Z, Huang W, Han B, Li J-L. N-Heterocyclic carbene and photoredox dual catalytic 1,2-boron migrative acylation. Sci Adv. 2024;10(30):Article eadn8401.
62.
Li Q-Z, Zou W-L, Yu Z-Y, Kou X-X, Liu Y-Q, Zhang X, He Y, Li J-L. Remote site-selective arene C–H functionalization enabled by N-heterocyclic carbene organocatalysis. Nat Catal. 2024;7(8):900–911.
63.
Li Q-Z, He M-H, Zeng R, Lei Y-Y, Yu Z-Y, Jiang M, Zhang X, Li J-L. Molecular editing of ketones through N-heterocyclic carbene and photo dual catalysis. J Am Chem Soc. 2024;146(32):22829–22839.
64.
Liu Y-Q, Fu L-L, Hong L-H, Kou X-X, Zhang X, Zeng R, Zhen Y-Q, Han B, Li J-L. N-Heterocyclic carbene organocatalysis enabled modular synthesis of fluorinated isoflavonoids to suppress proliferation and migration in breast cancer cells. Adv Sci. 2025;12(13):2413851.
65.
Liu D, Tu T, Zhang T, Nie G, Liao T, Ren S-C, Zhang X, Chi YG. Photocatalytic direct para-selective C−H amination of benzyl alcohols: Selectivity independent of side substituents. Angew Chem Int Ed. 2024;63(43):Article e202407293.
66.
Tanaka N, Zhu JL, Valencia OL, Schull CR, Scheidt KA. Cooperative carbene photocatalysis for β-amino ester synthesis. J Am Chem Soc. 2023;145(45):24486–24492.
67.
Chen S-C, Zhu Q, Cao Y, Li C, Guo Y, Kong L, Che J, Guo Z, Chen H, Zhang N, et al.Dealkenylative Ni-catalyzed cross-coupling enabled by tetrazine and photoexcitation. J Am Chem Soc. 2021;143(35):14046–14052.
68.
Chen S-C, Zhu Q, Chen H, Chen Z, Luo T. Pro-aromaticity enabled dealkenylative functionalizations via photo-excitation and oxidation. Chem Eur J. 2023;29(27):Article e202203425.
69.
Speckmeier E, Fischer TG, Zeitier K. A toolbox approach to construct broadly a applicable metal-free catalysts for photoredox chemistry: Deliberate tuning of redox potentials and importance of halogens in donor–acceptor cyanoarenes. J Am Chem Soc. 2018;140(45):15353–15365.
70.
Rourke MJ, Wang CT, Schull CR, Scheidt KA. Acyl azolium–photoredox-enabled synthesis of β-keto sulfides. ACS Catal. 2023;13(12):7987–7994.
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Year 2025 volume 8 Issue 12
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Article Info
doi: 10.34133/research.1010
  • Receive Date：2025-09-18
  • Online Date：2026-11-01
  • Published：2025-12-20
Article Data
Affiliations
History
  • Received：2025-09-18
  • Revised：2025-10-27
  • Accepted：2025-11-04
Funding
National Natural Science Foundation of China(22271028)
National Natural Science Foundation of China(22071011)
National Natural Science Foundation of China(22203010)
National Natural Science Foundation of China(22301023)
Department of Science and Technology of Sichuan Province(2023NSFSC2001)
Department of Science and Technology of Sichuan Province(2024NSFTD0023)
Special Project for Research and Development in Key areas of Guangdong Province(2022B1111050003)
Affiliations
    1Anti-infective Agent Creation Engineering Research Centre of Sichuan Province, Sichuan Industrial Institute of Antibiotics, School of Pharmacy, Chengdu University, Chengdu 610106, China.
    2Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry and Sichuan Province, and Sichuan Research Center for Drug Precision Industrial Technology, West China School of Pharmacy, Sichuan University, Chengdu 610041, China.

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表12种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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