Photoinduced Cyclopropanation of Olefins via Silicoborate-Mediated Radical Transfer

Photoinduced Cyclopropanation of Olefins via Silicoborate-Mediated Radical Transfer | 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 Search Search ADVANCED SEARCH SCROLL This is a preprint and has not been peer reviewed.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. 23 August 2025 V1 Latest version Share on Photoinduced Cyclopropanation of Olefins via Silicoborate-Mediated Radical Transfer Authors : Zhen-Ye Wu 0009-0003-5206-599X , Jiang-Hong Liu , Qing Liu , Li Hai , Tianle Huang , Zhong-Zhen Yang , and Yong Wu 0000-0003-0719-4963 [email protected] Authors Info & Affiliations https://doi.org/10.22541/au.175594534.41853785/v1 Published Tetrahedron Version of record Peer review timeline 167 views 157 downloads Contents Abstract Supplementary Material Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract This study develops a visible-light-driven, metal-free photocatalytic strategy that utilizes silicate reagents to generate reactive silicon-centered radicals. These radicals undergo efficient addition to olefins followed by strain-driven cyclization, enabling the synthesis of cyclopropane-functionalized silicon products. The method avoids transition-metal catalysts, demonstrates broad functional group tolerance, and operates under mild conditions. This approach provides a sustainable pathway for constructing strained carbocycles while overcoming limitations of traditional cyclopropanation methods. Cite this paper: Chin. J. Chem. 2024 , 42 , XXX—XXX. DOI: 10.1002/cjoc.202400XXX Photoinduced Cyclopropanation of Olefins via Silicoborate-Mediated Radical Transfer Zhen-Ye Wu, a Jiang-Hong Liu, a Qing Liu, a Li Hai, a Tian-Le Huang, a Zhong-Zhen Yang* , b and Yong Wu* , a a Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry and Department of Medicinal Chemistry, Sichuan Engineering Laboratory for Plant-Sourced Drug and Sichuan Research Center for Drug Precision Industrial Technology, West China School of Pharmacy, Sichuan University, No. 17 Southern Renmin Road, Chengdu, Sichuan 610041, People’s Republic of China. b Department of Pharmacy, West China Hospital, Sichuan University, Chengdu 610041, China Chengdu 610041 China. Metal-free photocatalysis | Silicon-centered radicals | Cyclopropanation | Strain-driven cyclization | Functional group tolerance | Sustainable synthesis | Radical cascade Comprehensive Summary This study develops a visible-light-driven, metal-free photocatalytic strategy that utilizes silicate reagents to generate reactive silicon-centered radicals. These radicals undergo efficient addition to olefins followed by strain-driven cyclization, enabling the synthesis of cyclopropane-functionalized silicon products. The method avoids transition-metal catalysts, demonstrates broad functional group tolerance, and operates under mild conditions. This approach provides a sustainable pathway for constructing strained carbocycles while overcoming limitations of traditional cyclopropanation methods. Background and Originality Content Organosilicon compounds find extensive applications in synthetic chemistry, pharmaceuticals, agrochemicals, and materials science due to their unique chemical and physical properties [1–7] . In chemistry, the C-Si bond is polarized, as silicon possesses a lower electronegativity than carbon. This polarity influences reactivity, facilitating selective transformations that are crucial in synthetic chemistry. Properties such as bond length, bond energy, and the ability to form stable yet reactive intermediates are exploited in numerous scientific and technological advances [8,9] . Silylboronates, powerful and versatile reagents for incorporating silicon and/or boron atoms into organic molecules [10–12] , have witnessed exponential growth in their utilization over the past few decades ( Scheme 1a ) [13,14] . Consequently, the synthetic applications of silyl radical precursors have garnered increasing attention and emerged as a prominent research focus in recent years [15–17] . In contrast to the requirement for excess oxidants or thermally induced hydrogen atom transfer (HAT) when using silanes as precursors to generate silyl radicals [18–20] , strategies employing photochemical, electrochemical, or base-activation methodologies to generate diverse silyl radicals from silyl boronates have been increasingly employed for constructing C–Si or C–X (X=B, O, ect) bonds [21–26] . Continued development of robust and versatile transformations, consequently, remains imperative to demonstrate the synthetic potential of silylboronates as privileged silyl radical precursors, particularly for constructing structurally complex architectures. In synthetic methodology, cyclization reactions represent a pivotal strategy for constructing carbocyclic and heterocyclic scaffolds prevalent in natural products and pharmaceuticals [27–30] . Strained three-membered rings—exemplified by cyclopropanes and epoxides—constitute privileged architectures due to their inherent ring strain, which engenders unique reactivity profiles and bioactivity [31–33] . Visible-light-mediated photoredox catalysis has emerged as a transformative platform for mediating single-electron transfer (SET) processes under mild and sustainable conditions. Compared to thermal approaches, this strategy operates at ambient temperature with exceptional functional group tolerance, while offering precise control through tunable photocatalysts (e.g., Ru/Ir complexes, organic dyes) to achieve enhanced reaction efficiency and selectivity [34–36] . Over the past decade, synthetic chemists have extensively explored the distinctive advantages of visible-light-mediated radical-polar crossover cyclization (RPCC) for assembling complex cyclic frameworks. Particularly in the synthesis of cyclopropane [37] , visible-light photocatalysis—as pioneered by Varinder K. Aggarwal [38] and Gary A. Molander [39] using diverse radical precursors—offers a sustainable alternative to transition-metal-catalyzed methods that generate environmentally hazardous residues (Scheme 1b). Nevertheless, the construction of silicon-functionalized cyclopropanes remains underexplored in this field [40] . Inspired by these precedents, we implement a synergistic strategy merging silylboronate-enabled radical-polar crossover cyclization (RPCC) with silyl radical chemistry to assemble gem-disubstituted silacyclopropanes from homoallylic substrates. Herein, we investigate the synergistic integration of photoredox catalysis and radical cascade reactions for constructing strained tricyclic architectures (Scheme 1c). Visible-light irradiation of borosilicate reagents generates silicon-centered radicals, which undergo regioselective addition to olefins followed by intramolecular cyclization, enabling efficient access to silicon-functionalized tricyclic products. This metal-free strategy establishes a sustainable and generalizable platform for synthesizing high-value strained carbocycles, circumventing limitations of conventional methods. Our findings provide mechanistic insights into the radical-polar crossover process while demonstrating broad synthetic utility. Scheme 1 Previous work and our work Results and Discussion We used methyl 4-(4-(tosyloxy)but-1-en-2-yl)benzoate ( 1a ) and triethyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)silane ( 2a ) as the reaction substrate model, systematically screened the reaction parameters, and optimized the reaction conditions. Initial evaluation of photocatalysts revealed that 4DPAIPN provided the highest yield of product d among various metal-based and organic photocatalysts tested ( Table 1 , entries 2-6). Subsequent solvent screening identified N-methyl-2-pyrrolidone (NMP) as the optimal reaction medium ( Table 1 , entries 7-10). Further investigation of base additives demonstrated that Cs 2 CO 3 significantly enhanced the reaction efficiency ( Table 1 , entries 11-15). Finally, optimization of irradiation conditions established that 450-455 nm light afforded optimal reaction outcomes (85%) ( Table 1 , entries 16-17). Additional experimental details and characterization data are provided in the Supporting Information. Table 1 Optimization of the reaction conditions 1 None 85 2 4CzIPN 65 3 Eosin Y 63 4 Ph-PTZ 55 5 [Ir(dtbbpy)(ppy) 2 ][PF 6 ] 52 6 Ru(bpy) 3 (PF 6 ) 2 56 7 1,4-Dioxane 50 8 EA 53 9 DMSO 60 10 DCM 0 11 K 3 PO 4 75 12 Na 2 CO 3 70 13 CsF 74 14 CsHCO 3 78 15 DIPEA 45 16 under 420-425 nm 65 17 under 390-395 nm 60 a Reaction conditions unless specified otherwise: 1a (0.10 mmol), 2a (0.15 mmol), 4DPAIPN (5 mmol%), Cs 2 CO 3 (0.1 mmol), NMP (2.0 mL) under 450-455nm LEDs at room temperature for 24 h, Ar atmosphere. b isolated yield. Subsequently, we investigated the substrate scope of this methodology (Scheme 2). Initial studies focused on para-substituted electron-withdrawing groups (EWGs) on the phenyl ring of the OTs substrate. These modifications consistently afforded the corresponding products 3a-3j in moderate to high yields (60%-95%). To elucidate the positional effects of substituents, meta-positioned methoxycarbonyl and ortho-positioned cyano groups Scheme 2 Scope of the substrate OTs reagent a,b a Reaction conditions unless specified otherwise: 1 (0.10 mmol), 2a (0.15 mmol), 4DPAIPN (5 mmol%), Cs 2 CO 3 (0.1 mmol), NMP (2.0 mL) under 450-455nm LEDs at room temperature for 24 h, Ar atmosphere. b isolated yield. were examined, yielding products 3k (76%) and 3l (63%) respectively. The methodology demonstrated good compatibility with diverse functional groups including acid amides, pyrrolidone and sulfonyl group providing products 3m-3p in satisfactory yields of 65%-81%. Notably, heteroaromatic systems proved viable substrates, with pyridine successfully yielding products 3q (75%) without significant yield reduction. Quinoline derivatives were also compatible with the reaction conditions, successfully affording the corresponding product 3r (45%). Incorporating silicon into drug molecules is a fascinating research field in medicinal chemistry, and it has the potential to create drugs with better performance than carbon-based drugs. To validate the pharmaceutical relevance of this transformation, we employed the indomethacin framework as a substrate. Remarkably, this complex medicinal scaffold underwent smooth conversion to product 3s while maintaining a favorable yield of 75%. However, when we attempted to use electron-donating group-substituted arenes as the substrate, obtaining the corresponding target product proved difficult ( 3t-3v ). This difficulty is likely attributable to the presence of the electron-donating group, which renders the formed intermediate insufficiently stable, thereby impeding the formation of the cyclopropanation product. Scheme 3 Scope of the substrate silicon reagent a,b a Reaction conditions unless specified otherwise: 1a (0.10 mmol), 2 (0.15 mmol), 4DPAIPN (5 mmol%), Cs 2 CO 3 (0.1 mmol), NMP (2.0 mL) under 450-455nm LEDs at room temperature for 24 h, Ar atmosphere. b isolated yield. Subsequently, the scope of silicon-based reagents was investigated (Scheme 3). The reaction demonstrated excellent tolerance toward both alkyl- and aryl-substituted silicon reagents, delivering products 4a-4k in moderate to high yields (56%-84%). To further explore the utility of the silylated products, we conducted downstream derivatization experiments. Transformations were separately performed targeting the silyl functional group and the arene functional group, yielding the corresponding transformed products (Scheme 4). Scheme 4 Product Derivatization. To elucidate the reaction mechanism, a series of control experiments were performed (Scheme 5). Mechanistic investigations revealed that the reaction exhibited markedly diminished product yields in the absence of a photocatalyst and base, with light irradiation identified as an essential requirement (Scheme 5a). And we conducted an On-Off experiment to verify whether continuous exposure to light is necessary (see SI). To further elucidate the electron transfer pathway, cyclic voltammetry was employed to determine the redox potentials of 4DPAIPN and 2a (Scheme 5b). Based on established electrochemical data for 4DPAIPN (reduction potential: −1.28 V vs SCE; oxidation potential: +1.10 V vs SCE) [41] and the measured potentials of 2a (reduction potential: −0.77 V vs SCE; oxidation potential: +0.72 V vs SCE), these electrochemical profiles collectively support a plausible single-electron transfer mechanism wherein 2a undergoes reduction via electron donation to the photoexcited 4DPAIPN. Fluorescence quenching experiments demonstrated that substrate 2a effectively quenches the excited state of photocatalyst 4DPAIPN (Scheme 4c). Scheme 5 Mechanism studies According to the reported articles [42–44] and mechanism experiments, the reaction mechanism was obtained (Scheme 5). Upon blue light irradiation, 4DPAIPN is photoexcited to its excited state 4DPAIPN*, which acts as a potent single-electron oxidant. The silicon reagent 2 combines with base to form an adduct, which then undergoes single-electron transfer (SET) with 4DPAIPN*, yielding a radical cation intermediate A and the reduced photocatalyst species 4DPAIPN ·− . Subsequently, A reacts with olefin 1 via radical addition, generating intermediate B. This intermediate B then participates in a second SET event with 4DPAIPN ·− , forming an anionic intermediate C. Finally, the carbon-negative center attacks the leaving group within the molecule, leading to cyclization and the formation of product 3. Scheme 6 Proposed mechanism Conclusions In summary, we have developed a visible-light-driven, metal-free photocatalytic strategy for the efficient synthesis of cyclopropane-functionalized silicon products. This method employs silicate reagents to generate reactive silicon-centered radicals, which undergo sequential intermolecular addition to olefins and intramolecular cyclization, to afford cyclopropane-functionalized silicon products. The protocol demonstrates remarkable advantages, including: (1) avoidance of transition-metal catalysts, (2) broad functional group tolerance as evidenced by successful application across dozens of substrates, and (3) excellent selectivity under mild reaction conditions. The current work provides a sustainable approach to constructing strained carbocycles while addressing several limitations associated with traditional cyclopropanation methods. The mechanistic insights gained from this study, particularly regarding the radical addition/cyclization cascade and the crucial role of the styrene precursor, may inspire further developments in radical-mediated ring-forming reactions. Experimental A glass tube equipped with a magnetic stir bar was charged with 1a (0.10 mmol), 4DPAIPN (0.005 mmol) and Cs 2 CO 3 (0.10 mmol). The tube was sealed and replaced with Ar over three times. NMP (2.0 mL) and silylboronic pinacol esters 2a (0.15 mmol) were added via syringe. The reaction mixture was stirred at room temperature for 24 h under 450-455nm LEDs irradiation. After complete consumption of the starting material 1a indicated by TLC, the mixture was transferred to a separating funnel. Then H 2 O (15 mL) was added, and the mixture was extracted with EtOAc (8 mL) for three times. The organic layer was dried with anhydrous Na 2 SO 4 and then concentrated under vacuum. The residue was purified by flash column chromatography on silica gel using ethyl acetate and petroleum ether (1:40 to 1:30, V/V) as the eluent to furnish the corresponding product 3a as a colorless oil in 85% yield. Other compounds ( 3b-3s, 4a-4k ) are processed in the same way. Supporting Information The supporting information for this article is available on the WWW under https://doi.org/10.1002/cjoc.202400xxx. Acknowledgement This work was supported by West China School of Medicine (West China Hospital) of Sichuan University “Qimingxing” Research Fund for Young Talents（HXQMX0092). References [1] Wang, M.; Hu, Z.; Yang, T.; Pei, H.; Zhang, F. A Dual Pesticide–Fertilizer Silicon-Base Nanocomposite to Synergistically Control Fungal Disease and Provide Nutrition. Environ. Sci.: Nano , 2023 , 10 , 3462–3475.[2] Zhou, H.; Han, J.T.; Nöthling, N.; Lindner, M.M.; Jenniches, J.; Kühn, C.; Tsuji, N.; Zhang, L.; List, B. Organocatalytic Asymmetric Synthesis of Si-Stereogenic Silyl Ethers. J. Am. Chem. Soc. , 2022 , 144 , 10156–10161.[3] Jaroniec, M. Organosilica the Conciliator. Nature , 2006 , 442 , 638–640.[4] Dai, S.; Li, M.; Yan, H.; Zhu, H.; Hu, H.; Zhang, Y.; Cheng, G.; Yuan, N.; Ding, J. Self-Healing Silicone Elastomer with Stable and High Adhesion in Harsh Environments. Langmuir , 2021 , 37 , 13696–13702.[5] Fanelli, R.; Chastel, A.; Previti, S.; Hindié, E.; Vimont, D.; Zanotti-Fregonara, P.; Fernandez, P.; Garrigue, P.; Lamare, F.; Schollhammer, R.; Balasse, L.; Guillet, B.; Rémond, E.; Morgat, C.; Cavelier, F. Silicon-Containing Neurotensin Analogues as Radiopharmaceuticals for NTS1-Positive Tumors Imaging. Bioconjugate Chem. , 2020 , 31 , 2339–2349.[6] Zhang, Z.; Li, L.; Xu, H.; Lee, C.-L.K.; Jia, Z.; Loh, T.-P. Silicon-Containing Thiol-Specific Bioconjugating Reagent. J. Am. Chem. Soc. , 2024 , 146 , 1776–1782.[7] Yamagishi, H.; Shimokawa, J.; Yorimitsu, H. Utilization of Silanols in Transition Metal-Catalyzed Organic Synthesis. ACS Catal. , 2023 , 13 , 7472–7487.[8] Wang, Q.; Meng, T.; Li, Y.; Yang, J.; Huang, B.; Ou, S.; Meng, C.; Zhang, S.; Tong, Y. Consecutive Chemical Bonds Reconstructing Surface Structure of Silicon Anode for High-Performance Lithium-Ion Battery. Energy Storage Materials , 2021 , 39 , 354–364.[9] Wang, X.; Wang, Z.-Y.; Zhang, X.; Xu, H.; Dai, H.-X. Construction of C(Sp2)–Si Bonds via Ligand-Promoted C–C Bonds Cleavage of Unstrained Ketones. Org. Lett. , 2022 , 24 , 7344–7349.[10] Shishido, R.; Uesugi, M.; Takahashi, R.; Mita, T.; Ishiyama, T.; Kubota, K.; Ito, H. General Synthesis of Trialkyl- and Dialkylarylsilylboranes: Versatile Silicon Nucleophiles in Organic Synthesis. J. Am. Chem. Soc. , 2020 , 142 , 14125–14133.[11] Boebel, T.A.; Hartwig, J.F. Iridium-Catalyzed Preparation of Silylboranes by Silane Borylation and Their Use in the Catalytic Borylation of Arenes. Organometallics , 2008 , 27 , 6013–6019.[12] Takeuchi, T.; Shishido, R.; Kubota, K.; Ito, H. Synthesis of Hydrosilylboronates via the Monoborylation of a Dihydrosilane Si–H Bond and Their Application for the Generation of Dialkylhydrosilyl Anions. Chem. Sci. , 2021 , 12 , 11799–11804.[13] Oestreich, M.; Hartmann, E.; Mewald, M. Activation of the Si–B Interelement Bond: Mechanism, Catalysis, and Synthesis. Chem. Rev. , 2013 , 113 , 402–441.[14] Wilkinson, J.R.; Nuyen, C.E.; Carpenter, T.S.; Harruff, S.R.; Van Hoveln, R. Copper-Catalyzed Carbon–Silicon Bond Formation. ACS Catal. , 2019 , 9 , 8961–8979.[15] Nazish, M.; Ding, Y.; Legendre, C.M.; Kumar, A.; Graw, N.; Schwederski, B.; Herbst-Irmer, R.; Parvathy, P.; Parameswaran, P.; Stalke, D.; Kaim, W.; Roesky, H.W. Excellent Yield of a Variety of Silicon-Boron Radicals and Their Reactivity. Dalton Trans. , 2022 , 51 , 11040–11047.[16] Yang, Y.; Song, R.-J.; Li, Y.; Ouyang, X.-H.; Li, J.-H.; He, D.-L. Oxidative Radical Divergent Si-Incorporation: Facile Access to Si-Containing Heterocycles. Chem. Commun. , 2018 , 54 , 1441–1444.[17] Ye, T.; Zhao, J.; Zheng, W.-X.; Zhang, J.; Wang, Z.; Zhang, F.-L. Synthesis of Structurally Diverse Silicon-Incorporated Indolines via Silyl Radical-Triggered Radical Cascade Reactions. Org. Chem. Front. , 2023 , 10 , 2165–2170.[18] Lan, Y.; Chang, X.-H.; Fan, P.; Shan, C.-C.; Liu, Z.-B.; Loh, T.-P.; Xu, Y.-H. Copper-Catalyzed Silylperoxidation Reaction of α,β-Unsaturated Ketones, Esters, Amides, and Conjugated Enynes. ACS Catal. , 2017 , 7 , 7120–7125.[19] Liu, L.; Klaasen, H.; Witteler, M.C.; Schulze Lammers, B.; Timmer, A.; Kong, H.; Mönig, H.; Gao, H.-Y.; Neugebauer, J.; Fuchs, H.; Studer, A. Polymerization of Silanes through Dehydrogenative Si–Si Bond Formation on Metal Surfaces. Nat. Chem. , 2021 , 13 , 350–357.[20] Lan, H.; Huo, X.; Jia, Y.; Wang, D. Silyl Radical Generation from Silylboronic Pinacol Esters through Substitution with Aminyl Radicals. Org. Lett. , 2024 , 26 , 1011–1016.[21] Kamio, S.; Nakamoto, M.; Yamagishi, T.; Oestreich, M.; Yoshida, H. Copper-Catalyzed Silylation of Aryl and Alkenyl Triflates with Silylboronic Esters Avoiding Base-Mediated Borylation. Chem. Commun. , 2024 , 60 , 6379–6382.[22] Ozawa, Y.; Koriyama, H.; Shiratori, Y.; Ito, H. Copper(I)-Catalyzed Regio- and Stereoselective Silaboration of Terminal Allenes. ACS Org. Inorg. Au , 2023 , 3 , 104–108.[23] Ke, J.; Liu, W.; Zhu, X.; Tan, X.; He, C. Electrochemical Radical Silyl-Oxygenation of Activated Alkenes. Angewandte Chemie International Edition , 2021 , 60 , 8744–8749.[24] Ding, C.; Ren, Y.; Yu, Y.; Yin, G. Ligand-Modulated Nickel-Catalyzed Regioselective Silylalkylation of Alkenes. Nat Commun , 2023 , 14 , 7670.[25] Asai, K.; Hirano, K.; Miura, M. Palladium-Catalyzed Benzylic Silylation of Diarylmethyl Carbonates with Silylboranes under Base-Free Conditions. European Journal of Organic Chemistry , 2022 , 2022 , e202101535.[26] Liu, Z.; Chen, J.; Lu, H.-X.; Li, X.; Gao, Y.; Coombs, J.R.; Goldfogel, M.J.; Engle, K.M. Palladium(0)-Catalyzed Directed Syn-1,2-Carboboration and -Silylation: Alkene Scope, Applications in Dearomatization, and Stereocontrol by a Chiral Auxiliary. Angewandte Chemie International Edition , 2019 , 58 , 17068–17073.[27] Li, S.; Dong, J. A Visible-Light-Induced Cyclization Reaction. COC , 2023 , 27 , 1020–1035.[28] Zhang, Q.; Xu, B.; Chen, D.; Wu, S.; Hu, X.; Zhang, X.; Yu, B.; Zhang, S.; Yang, Z.; Zhang, M.; Fang, Q. Structure–Activity Relationships of a Novel Cyclic Hexapeptide That Exhibits Multifunctional Opioid Agonism and Produces Potent Antinociceptive Activity. J. Med. Chem. , 2024 , 67 , 272–288.[29] Hasegawa, D.; Tsuji, A.; Greiner, L.C.; Arichi, N.; Inuki, S.; Ohno, H. Synthesis of Azocine-Fused Indoles via Gold(I)-Catalyzed Cyclization of Azido-Alkynes. J. Org. Chem. , 2025 , 90 , 925–930.[30] Aldeghi, M.; Malhotra, S.; Selwood, D.L.; Chan, A.W.E. Two- and Three-Dimensional Rings in Drugs. Chemical Biology & Drug Design , 2014 , 83 , 450–461.[31] Chen, D.; Cheng, Y.; Shi, L.; Gao, X.; Huang, Y.; Du, Z. Design, Synthesis, and Antimicrobial Activity of Amide Derivatives Containing Cyclopropane. Molecules , 2024 , 29 , 4124.[32] Ghosh, A.K.; Reddy, G.C.; Kovela, S.; Relitti, N.; Urabe, V.K.; Prichard, B.E.; Jurica, M.S. Enantioselective Synthesis of a Cyclopropane Derivative of Spliceostatin A and Evaluation of Bioactivity. Org. Lett. , 2018 , 20 , 7293–7297.[33] Jerhaoui, S.; Poutrel, P.; Djukic, J.-P.; Wencel-Delord, J.; Colobert, F. Stereospecific C–H Activation as a Key Step for the Asymmetric Synthesis of Various Biologically Active Cyclopropanes. Org. Chem. Front. , 2018 , 5 , 409–414.[34] Wang, H.; Xu, T. Dual Nickel- and Photoredox-Catalyzed Carbon-Carbon Bond Formations via Reductive Cross-Coupling Involving Organohalides. Chem Catalysis , 2024 , 4 , 100952.[35] Xiao, B.; Wu, K.; Zhang, M.; Hu, H.; Guo, X. Recent Advances in Photoredox/Chromium Dual-Catalyzed Carbonyl Addition Reactions: A Review. Advanced Synthesis & Catalysis , 2025 , 367 , e202401315.[36] Sinha, S.; Singh, P.P.; Kanaujia, S.; Singh, P.K.; Srivastava, V. Recent Advances of Photocatalytic Biochemical Transformations. Bioorganic Chemistry , 2025 , 157 , 108320.[37] Wang, N.; Zhao, J.-X.; Yue, J.-M. Total Synthesis of Cyclopropane-Containing Natural Products: Recent Progress (2016–2024). Org. Chem. Front. , 2025 , 12 , 2439–2456.[38] Shu, C.; Mega, R.S.; Andreassen, B.J.; Noble, A.; Aggarwal, V.K. Synthesis of Functionalized Cyclopropanes from Carboxylic Acids by a Radical Addition–Polar Cyclization Cascade. Angewandte Chemie International Edition , 2018 , 57 , 15430–15434.[39] Milligan, J.A.; Phelan, J.P.; Polites, V.C.; Kelly, C.B.; Molander, G.A. Radical/Polar Annulation Reactions (RPARs) Enable the Modular Construction of Cyclopropanes. Org. Lett. , 2018 , 20 , 6840–6844.[40] Dunn, J.; Dobbs, A.P. Synthesis and Reactions of Donor Cyclopropanes: Efficient Routes to Cis - and Trans -Tetrahydrofurans. Tetrahedron , 2015 , 71 , 7386–7414.[41] Singh, P.P.; Srivastava, V. Recent Advances in Using 4DPAIPN in Photocatalytic Transformations. Org. Biomol. Chem. , 2021 , 19 , 313–321.[42] Zeng, L.; Zhang, Y.; Hu, M.; He, D.-L.; Ouyang, X.-H.; Li, J.-H. Divergent Synthesis of (E)- and (Z)-Alkenones via Photoredox C(Sp3)–H Alkenylation–Dehydrogenation of o-Iodoarylalkanols with Alkynes. Org. Lett. , 2024 , 26 , 10096–10101.[43] Huang, F.-P.; Qin, W.-J.; Pan, X.-Y.; Yang, K.; Wang, K.; Teng, Q.-H. Visible-Light-Induced Chemodivergent Synthesis of Tetracyclic Quinazolinones and 3-Iminoisoindoliones via the Substrate Control Strategy. J. Org. Chem. , 2024 , 89 , 4395–4405.[44] Rueping, M.; Zhu, S.; Koenigs, R.M. Photoredox Catalyzed C–P Bond Forming Reactions—Visible Light Mediated Oxidative Phosphonylations of Amines. Chem. Commun. , 2011 , 47 , 8679–8681. Manuscript received: XXXX, 2024 Manuscript revised: XXXX, 2024 Manuscript accepted: XXXX, 2024 Version of record online: XXXX, 2024 Left to Right: (Top) Zhen-Ye Wu, Jiang-Hong Liu, Qing-Liu, Li Hai, (Bottom) Tian-Le Huang, Zhong-Zhen Yang and Yong Wu Entry for the Table of Contents This work outlines a metal-free photocatalytic strategy for the generation of silicon-centered radicals under visible light. It details their cascade addition-cyclization with olefins to access strained cyclopropane silicon products and highlights the system’s broad compatibility and sustainable profile. 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Keywords cyclopropanation metal-free photocatalysis radical cascade silicon-centered radicals sustainable synthesis Authors Affiliations Zhen-Ye Wu 0009-0003-5206-599X Sichuan University Key Laboratory of Drug Targeting and Drug Delivery System View all articles by this author Jiang-Hong Liu Sichuan University Key Laboratory of Drug Targeting and Drug Delivery System View all articles by this author Qing Liu Sichuan University Key Laboratory of Drug Targeting and Drug Delivery System View all articles by this author Li Hai Sichuan University Key Laboratory of Drug Targeting and Drug Delivery System View all articles by this author Tianle Huang Sichuan University Key Laboratory of Drug Targeting and Drug Delivery System View all articles by this author Zhong-Zhen Yang West China Hospital of Sichuan University View all articles by this author Yong Wu 0000-0003-0719-4963 [email protected] Sichuan University Key Laboratory of Drug Targeting and Drug Delivery System View all articles by this author Metrics & Citations Metrics Article Usage 167 views 157 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation Zhen-Ye Wu, Jiang-Hong Liu, Qing Liu, et al. Photoinduced Cyclopropanation of Olefins via Silicoborate-Mediated Radical Transfer. Authorea . 23 August 2025. DOI: https://doi.org/10.22541/au.175594534.41853785/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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