Decatungstate-Photocatalyzed Transfer Hydrogenation of Alkenes Using Alcohol as the Hydrogen Source

Decatungstate-Photocatalyzed Transfer Hydrogenation of Alkenes Using Alcohol as the Hydrogen Source | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Decatungstate-Photocatalyzed Transfer Hydrogenation of Alkenes Using Alcohol as the Hydrogen Source Cheuk-Wai So, Teng Zhang, Zheng-Feng Zhang, Xuan Lan, Si-Yi Li, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6566230/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 06 Jan, 2026 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract We present a simple and efficient photocatalytic method for the transfer hydrogenation of alkenes and alkynes using alcohol as the hydrogen source and inexpensive decatungstate as the photocatalyst. Our approach operates under mild, ambient conditions and demonstrates broad substrate compatibility, accommodating alkyl, aryl, and heteroatom-substituted alkenes and alkynes. To our knowledge, this study represents the first instance of using tungsten-based catalysts for the transfer hydrogenation of alkenes. Notably, the decatungstate/alcohol catalytic system exhibits excellent chemoselectivity, enabling selective hydrogenation of alkenes and alkynes even in the presence of reactive groups like ketones and carboxylic acids. These features highlight the considerable potential of this approach for practical and sustainable applications in organic synthesis. Physical sciences/Chemistry/Catalysis/Photocatalysis Physical sciences/Chemistry/Chemical synthesis/Synthetic chemistry methodology Figures Figure 1 Figure 2 Figure 3 Introduction Hydrogenation of alkenes is one of the most fundamental transformations in organic synthesis, typically requiring both a catalyst and a hydrogen source. 1 – 19 The most common hydrogen source is hydrogen gas (H₂), known for its 100% atom efficiency. However, safety concerns related to handling flammable and potentially explosive H₂ have led to the exploration of alternative hydrogen sources. 20 – 38 Photochemistry offers a novel approach for converting organic substrates into alternative hydrogen sources. One notable strategy involves photocatalytic reduction of alkenes to radical anions, which subsequently react with Brønsted-Lowry acids or solvents as proton donors to facilitate catalytic hydrogenation. 39 For instance, Guo and Houk et al. employed the strong acid TfOH and thioxanthone (TX) to photo-catalytically reduce α,β -unsaturated carbonyl compounds by using p -xylene (solvent) as the proton source (Fig. 1 a). 40 Similarly, Polyzos et al. described an iridium-catalyzed reduction of alkenes, followed by a reaction with Brønsted-Lowry acids to produce alkanes (Fig. 1 b). 41 However, this technique is limited by the reduction potential of the targeted alkenes. An alternative strategy was then developed, where iridium complexes were usually used to photo-catalytically generate radical cations to undergo hydrogen atom transfer (HAT) reactions with alkenes to form hydrogen-adduct carbon radicals. This is followed by either protonation with a proton source or addition with a hydrogen radical source to achieve catalytic hydrogenation. 42 – 46 For example, Wenger et al. demonstrated that an iridium photocatalyst mediated the HAT reaction between triethylamine (TEA) and alkenes, with subsequent radical addition completing alkene hydrogenation (Fig. 1 c). 45 Moreover, Studer and coworkers developed an iridium-catalyzed system for generating phosphine radical cations that activated water molecules to form a PR₃–H₂O radical cation intermediate, effectively utilizing both hydrogen atoms from H₂O in the alkene hydrogenation process through sequential heterolytic (H⁺) and homolytic (H•) O–H bond cleavages (Fig. 1 d). 46 Despite these advancements, replacing these rare and costly iridium photocatalysts with more abundant and inexpensive alternatives would significantly enhance the sustainability of hydrogenation processes. Alcohol is earth-abundant and sustainable, which would be a good candidate as a transfer hydrogenation reagent. However, the main difficulty for its use in the hydrogenation of alkenes originates from challenging homolytic cleavage of O–H and α-C–H bonds due to their high bond dissociation energies (BDE = ca 100 kcal/mol). 47 This is supported by currently reported photocatalysts, which solely mediate homolytic cleavage of the α-C–H bond in alcohols, generating reactive nucleophilic α-C-centered radicals (•CR 2 OH) for conjugate additions with Michael acceptors (Fig. 2 ). 48 – 53 We propose that if the homolytic cleavage of the α-C(sp³)–H bond of alcohol [R₂C(H)OH] generates a hydrogen radical (H•) and a relatively stable alcohol radical (•CR₂OH), this alcohol radical could undergo O–H bond cleavage, rather than reacting with the alkene, producing a C = O double bond in aldehydes or ketones (R₂C = O) and a second H•. These two hydrogen radicals could readily add across the C = C double bond, enabling effective alkene hydrogenation (Fig. 2 ). Transition metal-polyoxometalate hybrid clusters demonstrate good activity in mediating direct hydrogenation, 54 – 56 prompting us to explore whether an inexpensive and earth-abundant decatungstate anion, [W 10 O 32 ] 4− alone can be used as a photocatalyst for transfer hydrogenation. Upon irradiation, the decatungstate anion is excited to a reactive state capable of abstracting α-H atoms from alcohols, generating alcohol radicals (•CR₂OH) and reduced decatungstate species, H + [W 10 O 32 ]⁵ − . The alcohol radical undergoes homolytic cleavage of the O–H bond, forming an aldehyde or ketone and a hydrogen radical (H•). This hydrogen radical then reacts with the C = C double bond of an alkene (R₂C = CR₂), producing a carbon-centered radical (R₂(H)–C(•)R₂). The photocatalytic cycle is completed when this alkyl radical undergoes HAT with H + [W 10 O 32 ]⁵ − , yielding the hydrogenated alkene [R₂(H)–C(H)R₂] and regenerating the decatungstate anion [W 10 O 32 ]⁴ − . Herein, we report a simple, mild, and efficient strategy for alkene hydrogenation using alcohol as the hydrogen source and inexpensive decatungstate as the photocatalyst. To our knowledge, this study represents the first instance of using tungsten-based catalysts for the transfer hydrogenation of alkenes. Notably, the decatungstate/alcohol catalytic system exhibits excellent chemoselectivity, enabling selective hydrogenation of alkenes and alkynes even in the presence of reactive groups like ketones and carboxylic acids. These features highlight the significant potential of this approach for practical and sustainable applications in organic synthesis. Results Catalysis and Substrate Scope We initially investigated prenol 2a , a natural alcohol derived from biomass, as a hydrogen source for the transfer hydrogenation of 1,2-dibenzoylethylene ( 1a ) (Table 1 ). It is because the prenol-derived α-C radical (Me₂C = C(H)CH(•)OH) formed during α-C(sp³)–H bond activation can be stabilized by delocalization with the C = C double bond. 57 – 59 This stabilization likely reduces the reactivity of the radical toward 5a , thereby enabling the homolytic cleavage of the O–H bond to proceed efficiently. Upon 390 nm LED irradiation and with 5 mol% TBADT (tetrabutylammonium decatungstate) as the photocatalyst, the reaction yielded four types of products: the hydrogenated compound 4a (Isolated yield: 86%), aldehyde 3a , α-C(sp³)–H bond addition compound 5a (isolated yield: 5%), and a mixture of dimeric by-products arising from coupling of C = C double bond (Table S3 for their X-ray crystal structure). When TBADT was replaced with 2,4,6-triphenylpyrylium, a lower yield of compound 4a was observed. In contrast, using anthraquinone as a photocatalyst led to the formation of compound 5a (67%) as the major product. These findings speculate that the stability of the reduced photocatalyst, H + [photocatalyst] – , plays a key role in determining whether the prenol-derived α-C radical (Me 2 C = C(H)CH(•)OH) is capable of undergoing rearrangement to form 3a and H• before the HAT step by H + [photocatalyst] – occurs. The use of EosinY as a photocatalyst resulted in a mixture of dimeric by-products as major products, while 4a and 5a are minor products. EosinY was capable of photocatalytic C–H bond addition of 2-benzylidenemalononitrile with simple alcohols in quantitative conversion. 49 As such, we replaced compound 1a with 2-benzylidenemalononitrile, where EosinY catalyzed hydrogenation of 2-benzylidenemalononitrile with 2a to form [PhC(H) 2 C(H)(CN) 2 ] in 21% yield, along with a C–H bond addition product in 73% yield (Scheme S1). This supports our abovementioned hypothesis that prenol-derived α-C radical (Me₂C = C(H)CH(•)OH) has relatively higher stability, which allows hydrogenation to occur, even EosinY prefers to mediate C–H bond addition. Next, we evaluate the performance of primary and secondary alcohols in the TBADT-catalyzed transfer hydrogenation of 1,2-dibenzoylethylene (Table 1 ). Prenol is the most effective, yielding 4a with the highest isolated yield. Allyl alcohol ( 2b ) also performed well, producing 4a in 79% isolated yield, while natural alcohol geraniol ( 2c ) afforded a comparable yield of 81%. Benzyl alcohol ( 2d ) and pyridin-2-ylmethanol ( 2e ) were efficient hydrogen donors, delivering isolated yields of 72% and 76%, respectively. Secondary alcohols such as 1-phenylethanol ( 2f ) and 1-(pyridin-4-yl)ethan-1-ol ( 2g ) achieved similarly high isolated yields (75% and 86%, respectively). Furan-2-ylmethanol ( 2h ) is cumbersome in the catalysis based on the moderate isolated yield of 4a (48%). Conversely, simple alcohols such as ethanol ( 2i) and 2-propanol ( 2j) produced lower isolated yields of 4a (26% and 29%). These findings show that the nucleophilic alcohol α-C-centered radicals (•CR 2 OH) contain an unsaturated moiety (R = benzene, pyridine or alkene), having high efficiency in the hydrogenation of alkene, probably due to the stabilization of the radical, allowing homolytic O–H bond cleavage. Overall, these results demonstrate the feasibility of using a diverse array of primary and secondary alcohols as hydrogen sources in TBADT-mediated transfer hydrogenation, emphasizing the robustness and versatility of this approach. With optimized reaction conditions established, we explored the substrate scope of olefins, as summarized in Table 2 . The hydrogenation of 1,2-dibenzoylethylene ( 1a ) with prenol produced 4a in an excellent isolated yield (86%). Encouraged by this result, we explored α,β-unsaturated carbonyl compounds. To our delight, the 4-phenyl-3-buten-2-one ( 1b ) reacted efficiently to produce 4-phenylbutan-2-one ( 4b ) in 76% isolated yield. Derivatives of 1b with electron-donating and electron-withdrawing substituents at different positions ortho - ( 1c , o -Me; 1d , o -F), meta - ( 1e , m -OMe), and para - ( 1f , p -OMe; 1g , p -OH; 1h , p -Cl; 1i , p -F; 1j , p -CF 3 ) were successfully hydrogenated, yielding the corresponding products ( 4c - 4j ) in moderate to high isolated yields (54–85%). The results revealed that the electron-rich substituents at the β position ( 1c , 1e, 1f, 1g ) led to slightly reduced isolated yields (54–63%). Replacing the phenyl group with a methyl ( 1k ) or α -naphthyl substituent ( 1l ) did not significantly affect product yields, producing 4k and 4l in 66% and 71% isolated yields, respectively. However, the hydrogenation of 1m , which contains a pyridine substituent, led to reductive coupling instead of hydrogenation to form 6m in 91% isolated yield. Moreover, 1-phenylbuten-1-one ( 1n ) and 1,3-diphenylpropen-1-one ( 1o ) were hydrogenated, giving a moderate isolated yield of 41% and 32%, respectively. Carboxylic acid and ester substituents enhanced reactivity, yielding 4p - 4s in 67–87% isolated yields. Terminal olefins, namely 3-buten-2-one ( 1t ) and 1-phenylprop-2-en-1-one ( 1u ) were effectively hydrogenated leading to 4t (86%) and 4u (84%) in good isolated yields, respectively. When more substituted terminal olefin, namely, 3-methylbut-3-en-2-one ( 1v ) was hydrogenated, the isolated yield of 4v dropped to 64%. Cycloenone 1w and more substituted derivative 1x also reacted to form cyclohexanones 4w (76%) and 4x (43%), respectively. Next, reactive functional groups namely ester, nitro, and cyano groups in 1y – 1ab were well compatible in catalysis (38–46%). Pyridine substituent promoted the hydrogenation, where 1,2-di(4-pyridyl)ethylene ( 1ac ) was converted into 4ac with an excellent isolated yield of 94%. Remarkably, the anti-lymphoma and leukemia cancer drug, namely Ibrutinib ( 1ad ) was hydrogenated to produce 4ad in 56% isolated yield, demonstrating the utility of this catalytic method in the late-stage functionalization of pharmaceutical agents. Subsequently, the hydrogenation of other types of unsaturated bonds were tested. N = N double bonds ( 1ae) were efficiently reduced under optimized conditions, yielding 4ae in 86%. It appears that the N lone pair of electrons does not affect the reaction mechanism. Phenylacetylene and its derivatives with various substituents ( 9a - 9h ) were efficiently converted to the corresponding terminal olefins ( 10a - 10h ) in 64–91% isolated yields. Alkynes with carbonyl groups underwent double hydrogenation to directly form alkanes ( 4a - 4u , 69–83%), indicating that the carbonyl groups facilitate hydrogenation. Mechanistic Investigations To clarify the catalytic mechanism, deuterated benzyl alcohols PhCH 2 OD and PhCD 2 OH were reacted with 1ac (Fig. 3 a). These reactions resulted in a 1:1 molar ratio of 4ac- d and 3d , and a 1:1 molar ratio of 4ac- d and 3d- d , respectively (Figure S4 and S5), confirming that alcohols are the sole hydrogen source. Moreover, introducing the radical scavenger TEMPO (1 equiv.) significantly inhibited the formation of 4ac as the H• and alcohol α-C centered radicals were quenched by TEMPO (Figure S7 and S8 showing the presence of the quenched radicals in HRMS). These findings indicate that the mechanism involves the activation of the α-C(sp 3 )–H bond of alcohols to form alcohol α-C-centered radicals in the first step. To further understand why the alcohol α-C-centered radical undergoes O-H bond cleavage rather than directly adding to the alkene during catalysis, density functional theory (DFT) calculations were performed using butenone 1t and prenol α-C-centered radical R2a as model substrates (Fig. 3 b). Two potential hydrogenation pathways were explored. In Path I , the R2a undergoes homolytic cleavage of its O–H bond and addition of H• at the β -position of 1t via TS-A (ΔG = 23.3 kcal/mol) to form thermodynamic intermediates A and 3a (ΔG = -8.3 kcal/mol). In contrast, the addition of H• at the α -position of 1t is infeasible due to the high kinetic barrier ( Path II , TS-B: ΔG = 43.8 kcal/mol). In the C–C bond formation pathway ( Path III ), R2a adds to 1t via TS-C (ΔG = 13.6 kcal/mol), forming kinetic intermediate C (ΔG = -5.8 kcal/mol). Based on TS-A and TS-C , both Path I and Path III are viable at room temperature, but hydrogenation is more favorable due to the thermodynamic intermediates A and 3a . It is consistent with experimental observations, where decatungstate-photocatalyzed hydrogenation of butenone with prenol requires prolonged reaction times at room temperature (> 12 hours), but proceeds significantly faster at higher temperatures (70°C, 6 hours). As shown in Table 1 a, TBADT and 2,4,6-triphenylpyrylium selectively catalyze hydrogenation, while anthraquinone promotes C–H bond addition. These results indicate that the reduced photocatalyst H + [W 10 O 32 ] 5− , which is formed by the α-C(sp 3 )–H bond activation of alcohols, favors Path I to complete the catalysis. Based on the experimental data and DFT calculations, a plausible mechanism for decatungstate-photocatalyzed transfer hydrogenation of alkenes using alcohol as the hydrogen source is proposed (Fig. 3 c). Upon 390 nm LED light irradiation, decatungstate transitions to an excited state and rapidly relaxes to its reactive state w O . This w O species initiates the process by transferring a hydrogen atom to produce a carbon-centered alcohol radical, •CROH ( I ). 60 – 62 The resulting radical undergoes first hydrogen atom transfer ( Path I ) to alkene, forming a radical intermediate III and aldehyde/ketone ( II ). The intermediate III subsequently undergoes a second HAT with H + [W 10 O 32 ] 5− , producing the final alkane product ( IV ) and regenerating the starting catalyst [W 10 O 32 ] 4− to close the catalytic cycle. In addition, the alcohol radical •CROH ( I ) can undergo conjugate addition with alkenes via Path III to generate intermediate V , which reacts with H + [W 10 O 32 ] 5− to yield a byproduct VI . In summary, we have developed a simple, mild, and efficient photocatalytic method for the transfer hydrogenation of alkenes using alcohols as the hydrogen source and inexpensive decatungstate as the photocatalyst. This method demonstrates broad substrate compatibility, high chemoselectivity, and practicality under ambient conditions. Mechanistic studies reveal that the hydrogenation proceeds via a radical-mediated pathway involving the sequential homolytic cleavage of α-C(sp³)–H and O–H bonds in alcohols. DFT calculations further confirmed that the hydrogenation pathway is more exothermic than the side α-C(sp³)–H functionalization route, indicating it is thermodynamically favored, consistent with experimental observations. These findings highlight the significant potential of the decatungstate/alcohol catalytic system in practical organic synthesis, offering a sustainable approach for alkene hydrogenation. Methods For the detailed experimental methods described in this manuscript, please refer to the Supplementary Information. Declarations Data Availability CCDC-2384191 (for 6m ), 2384192 (for 4a ), and 2402528-2402530 (for 6a, 7 and 8 ), contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data request/cif, or by emailing [email protected] , or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: + 44 1223 336033. Competing interests The authors declare no competing interests. Supplementary Information Experimental procedures and supporting data (mechanistic studies, DFT calculations, compound characterization data, and NMR spectra) can be found in the Supporting Information. Author contributions T. Z., Y. R. Chi, L. Wu, and C.-W. S. conceived and designed the project. T. Z., X. L., and S.-Y. L. performed and analyzed the chemical experiments. Z.-F. Z. and M.-D. S. performed and analyzed the DFT calculations. T. Z., L. Wu, and C.-W. S. analyzed the data and prepared the manuscript. All the authors reviewed the manuscript. Acknowledgements This work is supported by the Ministry of Education Singapore, AcRF Tier 2 (MOE2019-T2-2-129) and A*STAR MTC Individual Research Grants (M21K2c0117) for the financial support. References Verendel JJ, Pàmies O, Diéguez M, Andersson PG (2014) Asymmetric Hydrogenation of Olefins Using Chiral Crabtree-type Catalysts: Scope and Limitations. Chem Rev 114:2130–2169 Wang D-S, Chen Q-A, Lu S-M, Zhou Y-G (2012) Asymmetric Hydrogenation of Heteroarenes and Arenes. Chem Rev 112:2557–2590 Qu R, Junge K, Beller M (2023) Hydrogenation of Carboxylic Acids, Esters, and Related Compounds over Heterogeneous Catalysts: A Step toward Sustainable and Carbon-Neutral Processes. Chem Rev 123:1103–1165 Cabré A, Verdaguer X, Riera A (2022) Recent Advances in the Enantioselective Synthesis of Chiral Amines via Transition Metal-Catalyzed Asymmetric Hydrogenation. Chem Rev 122:269–339 Wen J, Wang F, Zhang X (2021) Asymmetric Hydrogenation Catalyzed by First-row Transition Metal Complexes. Chem Soc Rev 50:3211–3237 Lückemeier L, Pierau M, Glorius F (2023) Asymmetric arene hydrogenation: towards sustainability and application. Chem Soc Rev 52:4996–5012 Kumar A, Daw P, Milstein D (2022) Homogeneous Catalysis for Sustainable Energy: Hydrogen and Methanol Economies, Fuels from Biomass, and Related Topics. Chem Rev 122:385–441 Lam J, Szkop K, Mosaferi E, Stephan DW (2019) FLP Catalysis: Main Group Hydrogenations of Organic Unsaturated Substrates. Chem Soc Rev 48:3592–3612 Kraft S, Ryan K, Kargbo RB (2017) Recent Advances in Asymmetric Hydrogenation of Tetrasubstituted Olefins. J Am Chem Soc 139:11630–11641 Ding Z, Luo Y, Yuan Q, Wang G, Yu Z, Zhao M, Liu D, Zhang W (2024) Ru-Catalyzed Asymmetric Hydrogenation of α,β-Unsaturated γ-Lactams. J. Am. Chem. Soc. 146, 25312 – 25320 Friedfeld MR, Zhong H, Ruck RT, Shevlin M, Chirik PJ (2018) Cobalt-catalyzed asymmetric hydrogenation of enamides enabled by single-electron reduction. Science 360, 888 – 893 Margarita C, Andersson PG (2017) Evolution and Prospects of the Asymmetric Hydrogenation of Unfunctionalized Olefins. J Am Chem Soc 139:1346–1356 Davies AT, Pickett PM, Slawin AMZ, Smith AD (2014) Asymmetric Synthesis of Tri- and Tetrasubstituted Trifluoromethyl Dihydropyranones from α–Aroyloxyaldehydes via NHC Redox Catalysis. ACS Catal. 4, 2696 – 2700 Kim AN, Stoltz BM (2020) Recent Advances in Homogeneous Catalysts for the Asymmetric Hydrogenation of Heteroarenes. ACS Catal 10:13834–13851 Wei H, Luo Y, Li J, Chen J, Gridnev ID, Zhang W (2025) Enantioselective Synthesis of Chiral β 2 –Amino Phosphorus Derivatives via Nickel-Catalyzed Asymmetric Hydrogenation. J Am Chem Soc 147:342–352 Mas-Rosellό J, Smejkal T, Cramer N (2020) Iridium-catalyzed acid-assisted asymmetric hydrogenation of oximes to hydroxylamines. Science 368, 1098 – 1102 Yang F, Xie J-H, Zhou Q-L (2023) Highly Efficient Asymmetric Hydrogenation Catalyzed by Iridium Complexes with Tridentate Chiral Spiro Aminophosphine Ligands. Acc Chem Res 56:332–349 Chakrabortty S, Konieczny K, de Zwart FJ, Bobylev EO, Baráth E, Tin S, Müller BH, Reek JNH, de Bruin B, de Vries JG (2023) Cobalt-Catalyzed Enantioselective Hydrogenation of Trisubstituted Carbocyclic Olefins: An Access to Chiral Cyclic Amides. Angew Chem Int Ed 62:e202301329 Wiesenfeldt MP, Nairoukh Z, Li W, Glorius F (2017) Hydrogenation of Fluoroarenes: Direct Access to All-cis-(multi)-fluorinated Cycloalkanes. Science 357:908–912 Wang D, Astruc D (2015) The Golden Age of Transfer Hydrogenation. Chem Rev 115:6621–6686 Santana CG, Krische MJ (2021) From Hydrogenation to Transfer Hydrogenation to Hydrogen Auto-Transfer in Enantioselective Metal-Catalyzed Carbonyl Reductive Coupling: Past, Present, and Future. ACS Catal 11:5572–5585 Pang M, Chen J-Y, Zhang S, Liao R-Z, Tung C-H, Wang W (2020) Controlled Partial Transfer Hydrogenation of Quinolines by Cobalt-Amido Cooperative Catalysis. Nat Commun 11:1249 Lau S, Gasperini D, Webster RL (2021) Amine-Boranes as Transfer Hydrogenation and Hydrogenation Reagents: A Mechanistic Perspective. Angew Chem Int Ed 60:14272–14294 Zhou Q, Meng W, Yang J, Du HA (2018) Continuously Regenerable Chiral Ammonia Borane for Asymmetric Transfer Hydrogenations. Angew Chem Int Ed 57:12111–12115 Cummings SP, Le T-N, Fernandez GE, Quiambao LG, Stokes BJ (2016) Tetrahydroxydiboron-Mediated Palladium-Catalyzed Transfer Hydrogenation and Deuteriation of Alkenes and Alkynes Using Water as the Stoichiometric H or D Atom Donor. J Am Chem Soc 138:6107–6110 Xu H, Yang P, Chuanprasit P, Hirao H, Zhou JS (2015) Nickel-Catalyzed asymmetric transfer hydrogenation of hydrazones and other ketimines. Angew Chem Int Ed 54:5112–5116 Zhao E, Li M, Xu B, Wang X-L, Jing Y, Ma D, Mitchell S, Pérez-Ramírez J, Chen Z (2022) Transfer Hydrogenation with a Carbon-Nitride-Supported Palladium Single-Atom Photocatalyst and Water as a Proton Source. Angew Chem Int Ed 61:e202207410 Sun Y, Wang C, Yang P, Yue J-Y, Xu C, Zhou JS, Tang B (2023) Hydrogen bond enhanced enantioselectivity in the Nickel-catalyzed transfer hydrogenation of α-substituted acrylic acid with formic acid. ACS Catal 13:14213–14220 Broggi J, Jurčík V, Songis O, Poater A, Cavallo L, Slawin AMZ, Cazin CS (2013) J. The Isolation of [Pd{OC(O)H}(H)(NHC)(PR 3 )] (NHC = N-Heterocyclic Carbene) and Its Role in Alkene and Alkyne Reductions Using Formic Acid. J Am Chem Soc 135:4588–4591 Wang F, Yang T, Wu T, Zheng L-S, Yin C, Shi Y, Ye X-Y, Chen G-Q, Zhang X (2021) Asymmetric Transfer Hydrogenation of α–Substituted-β-Keto Carbonitriles via Dynamic Kinetic Resolution. J Am Chem Soc 143:2477–2483 Lin Y, Xu G, Tang W (2024) Chiral Polymeric Diamine Ligands for Iridium-Catalyzed Asymmetric Transfer Hydrogenation. J Am Chem Soc 146:27736–27744 Wu J, Chen Z, Barnard JH, Gunasekar R, Pu C, Wu X, Zhang S, Ruan J, Xiao J (2022) Synthesis of Chiral Piperidines from Pyridinium Salts via Rhodium-Catalysed Transfer Hydrogenation. Nat Catal 5:982–992 Lan S, Huang H, Liu W, Xu C, Lei X, Dong W, Liu J, Yang S, Cotman AE, Zhang Q, Fang X (2024) Asymmetric Transfer Hydrogenation of Cyclobutenediones. J Am Chem Soc 146:4942–4957 Kattamuri PV, West JG (2020) Hydrogenation of Alkenes via Cooperative Hydrogen Atom Transfer. J Am Chem Soc 142:19316–19326 Liu X, Huang L, Ma Y, She G, Zhou P, Zhu L, Zhang Z (2024) Enable Biomass-Derived Alcohols Mediated Alkylation and Transfer Hydrogenation. Nat Commun 15:7012 Luo G-G, Pan Z-H, Han B-L, Dong G-L, Deng C-L, Azam M, Tao Y-W, He J, Sun C-F, Sun D (2023) Total Structure, Electronic Structure and Catalytic Hydrogenation Activity of Metal-Deficient Chiral Polyhydride Cu57 Nanoclusters. Angew Chem Int Ed 62:e202306849 Qian L, Yu C, Gan L, Tang X, Wang Y, Liu G, Leng X, Sun Z, Guo Y, Xue X-S, Huang Z (2024) Iridium-Catalyzed Enantioselective Transfer Hydrogenation of 1,1-Dialkylethenes with Ethanol: Scope and Mechanism. J Am Chem Soc 146:3427–3437 Zuo W, Lough AJ, Li YF, Morris RH (2013) Amine(imine)diphosphine Iron Catalysts for Asymmetric Transfer Hydrogenation of Ketones and Imines. Science 342:1080–1083 Pac C, Ihama M, Yasuda M, Miyauchi Y, Sakurai H (1981) Tris(2,2'-Bipyridine)Ruthenium(2+)-Mediated Photoreduction of Olefins with 1-Benzyl-1,4-Dihydronicotinamide: a Mechanistic Probe for Electron-Transfer Reactions of NAD(P)H-Model Compounds. J Am Chem Soc 103:6495–6497 Kang W-J, Li B, Duan M, Pan G, Sun W, Ding A, Zhang Y, Houk KN, Guo H (2022) Discovery of a Thioxanthone-TfOH Complex as a Photoredox Catalyst for Hydrogenation of Alkenes Using p-Xylene as both Electron and Hydrogen Sources. Angew Chem Int Ed 61:e202211562 Czyz ML, Taylor MS, Horngren TH, Polyzos A (2021) Reductive Activation and Hydrofunctionalization of Olefins by Multiphoton Tandem Photoredox Catalysis. ACS Catal 11:5472–5480 Larionova NA, Ondozabal JM, Cambeiro XC (2021) Reduction of Electron-Deficient Alkenes Enabled by a Photoinduced Hydrogen Atom Transfer. Adv Synth Catal 363:558–564 Park Y, Tian L, Kim S, Pabst TP, Kim J, Scholes GD, Chirik PJ (2022) Visible-Light-Driven, Iridium-Catalyzed Hydrogen Atom Transfer: Mechanistic Studies, Identification of Intermediates, and Catalyst Improvements. JACS Au 2:407–418 Zhou W, Dmitriev IA, Melchiorre P (2023) Reductive Cross-Coupling of Olefins via a Radical Pathway. J Am Chem Soc 145:25098–25102 Schreier MR, Pfund B, Guo X, Wenger OS (2020) Phototriggered hydrogen atom transfer from an iridium hydride complex to unactivated olefins. Chem Sci 11:8582–8594 Zhang J, Mück-Lichtenfeld C, Studer A (2023) Photocatalytic Phosphine-Mediated Water Activation for Radical Hydrogenation. Nature 619:506–513 Luo YR (2007) Comprehensive Handbook of Chemical Bond Energies. CRC, Boca Raton, FL Jeffrey JL, Terrett JA, MacMillan DWC (2015) O-H Hydrogen Bonding Promotes H-Atom Transfer from C – H Bonds for C-Alkylation of Alcohols. Science 349:1532–1536 Fan X, Rong J, Wu H, Zhou Q, Deng H, Tan J, Da, Xue C, Wu L, Tao H, Wu J (2018) Eosin Y as a Direct Hydrogen-Atom Transfer Photocatalyst for the Functionalization of C – H Bonds. Angew Chem Int Ed 57:8514–8518 Liu L, Liu J, Liang X-A, Wang S, Lei A (2019) Visible Light-Induced Direct α-C – H Functionalization of Alcohols. Nat Commun 10:467–453 Paul S, Filippini D, Ficarra F, Melnychenko H, Janot C, Silvi M (2023) Oxetane Synthesis via Alcohol C – H Functionalization. J Am Chem Soc 145:15688–15694 Twilton J, Christensen M, DiRocco DA, Ruck RT, Davies IW, MacMillan DWC (2018) Selective Hydrogen Atom Abstraction through Induced Bond Polarization: Direct α-Arylation of Alcohols through Photoredox, HAT, and Nickel Catalysis. Angew Chem Int Ed 57:5369–5373 Capaldo L, Merli D, Fagnoni M, Ravelli D (2019) Visible Light Uranyl Photocatalysis: Direct C – H to C – C Bond Conversion. ACS Catal 9:3054–3058 Wang S-S, Yang G-Y (2015) Recent Advances in Polyoxometalate-Catalyzed Reactions. Chem Rev 115:4893–4962 Zhang M, Li Z, Feng Y, Xin X, Yang G-Y, Lv H (2023) Highly Selective Hydrogenolysis of Lignin Β-O-4 Models by A Coupled Polyoxometalate/Cds Photocatalytic System. Green Chem 25:10091–10100 Li S, Ma Y, Zhao Y, Liu R, Zhao Y, Dai X, Ma N, Streb C, Chen X (2023) Hydrogenation Catalysis by Hydrogen Spillover on Platinum-Functionalized Heterogeneous Boronic Acid-Polyoxometalates. Angew Chem Int Ed 62:e202314999 Gobbi A, Frenking G (1994) Resonance Stabilization in Allyl Cation, Radical, and Anion. J Am Chem Soc 116:9275–9286 Mo Y, Lin Z, Wu W, Zhang Q (1996) Delocalization in Allyl Cation, Radical, and Anion. J Phys Chem 100:6469–6474 Hioe J, Zipse H (2010) Radical Stability and Its Role in Synthesis and Catalysis. Org Biomol Chem 8:3609–3617 Tanielian C, Decatungstate, Photocatalysis (1998) Coord. Chem. Rev. 178 – 180, 1165 – 1181 Laudadio G, Deng Y, van der Wal K, Ravelli D, Nunõ M, Fagnoni M, Guthrie D, Sun Y, Noël T (2020) C(sp 3 )-H Functionalizations of Light Hydrocarbons Using Decatungstate Photocatalysis in Flow. Science 369:92–96 Ravelli D, Fagnoni M, Fukuyama T, Nishikawa T, Ryu I (2018) Site-Selective C – H Functionalization by Decatungstate Anion Photocatalysis: Synergistic Control by Polar and Steric Effects Expands the Reaction Scope. ACS Catal 8:701–713 Tables Tables 1 and 2 are available in the Supplementary Files section. Additional Declarations There is NO Competing Interest. Supplementary Files 4a.cif cif file of compound 4a 6m.cif cif file of compound 6m 6a.cif cif file of compound 6a 7.cif cif file of compound 7 8.cif cif file of compound 8 SupportingInformationPOMhydrogenationCWSorevised.pdf Supporting Information Tables.docx Cite Share Download PDF Status: Published Journal Publication published 06 Jan, 2026 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6566230","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":455454679,"identity":"403bf553-f6a1-4f3f-b3d5-8aa38657e4f4","order_by":0,"name":"Cheuk-Wai So","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAu0lEQVRIiWNgGAWjYBAC/hnpDxg+QNgGxGmRuJFjwDgDoppILQYROQzMPKRpkchhfGy7409iA3vzNgmGP7VEaJFOf2yce8YgsYHnWJkEY9txYrQkmEnntgG1SOSYSTA2HCNSiyVIi/wbM6DDiNES/8BMmhFsCw9QC1sNYS0Sd94YG/a2GRu38aQVWyS2HSCsBRiVDx/8bJOT7Wc/vPHGhz91hLXAARuISGA4TIIWKCDFllEwCkbBKBgpAABuhTbBPkhgTQAAAABJRU5ErkJggg==","orcid":"https://orcid.org/0000-0003-4816-9801","institution":"Nanyang Technological University","correspondingAuthor":true,"prefix":"","firstName":"Cheuk-Wai","middleName":"","lastName":"So","suffix":""},{"id":455454680,"identity":"e5795213-f46d-4792-b44d-76f7922e128b","order_by":1,"name":"Teng Zhang","email":"","orcid":"","institution":"Nanyang Technological University","correspondingAuthor":false,"prefix":"","firstName":"Teng","middleName":"","lastName":"Zhang","suffix":""},{"id":455454681,"identity":"786e4b10-3086-4b98-b723-8ffdd7f5cecc","order_by":2,"name":"Zheng-Feng Zhang","email":"","orcid":"","institution":"National Chiayi University","correspondingAuthor":false,"prefix":"","firstName":"Zheng-Feng","middleName":"","lastName":"Zhang","suffix":""},{"id":455454682,"identity":"eaf154f3-5248-4da0-b04c-ea43a5bfe478","order_by":3,"name":"Xuan Lan","email":"","orcid":"","institution":"Zhejiang Normal University","correspondingAuthor":false,"prefix":"","firstName":"Xuan","middleName":"","lastName":"Lan","suffix":""},{"id":455454683,"identity":"a468944b-8eac-423e-a095-3481ebcfc60f","order_by":4,"name":"Si-Yi Li","email":"","orcid":"","institution":"Zhejiang Normal University","correspondingAuthor":false,"prefix":"","firstName":"Si-Yi","middleName":"","lastName":"Li","suffix":""},{"id":455454684,"identity":"bf45dcc8-1c36-45dd-9462-3b35592bb9a3","order_by":5,"name":"Ming-Der Su","email":"","orcid":"","institution":"National Chiayi University","correspondingAuthor":false,"prefix":"","firstName":"Ming-Der","middleName":"","lastName":"Su","suffix":""},{"id":455454685,"identity":"52134cff-9ba1-4354-9e76-514cab6b8951","order_by":6,"name":"Yonggui Robin Chi","email":"","orcid":"https://orcid.org/0000-0003-0573-257X","institution":"Nanyang Technological University","correspondingAuthor":false,"prefix":"","firstName":"Yonggui","middleName":"Robin","lastName":"Chi","suffix":""},{"id":455454686,"identity":"7a773161-17ba-4b04-89cd-73629a343ec6","order_by":7,"name":"Lixin Wu","email":"","orcid":"https://orcid.org/0000-0002-4735-8558","institution":"Jilin University","correspondingAuthor":false,"prefix":"","firstName":"Lixin","middleName":"","lastName":"Wu","suffix":""}],"badges":[],"createdAt":"2025-04-30 15:10:31","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6566230/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6566230/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41467-025-67482-1","type":"published","date":"2026-01-06T05:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":82672632,"identity":"4f06a924-e392-4154-a096-e1a0d3dd5df8","added_by":"auto","created_at":"2025-05-14 03:20:01","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":46822,"visible":true,"origin":"","legend":"\u003cp\u003eThe previous work on photocatalytic transfer hydrogenation reactions.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-6566230/v1/ed4711b1fc15883b45080ab1.png"},{"id":82673435,"identity":"6dfd264c-f07e-4e80-a4e9-1f5648860500","added_by":"auto","created_at":"2025-05-14 03:28:01","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":28610,"visible":true,"origin":"","legend":"\u003cp\u003eThe designed photocatalytic transfer hydrogenation of alkenes using alcohol as the hydrogen source.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-6566230/v1/5cea4afcf35ce3500a1a9950.png"},{"id":82673436,"identity":"4bf690ec-d342-402a-94e8-016d291fb63d","added_by":"auto","created_at":"2025-05-14 03:28:01","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":87374,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Deuteration and radical capture experiments; (b) Calculated Gibbs free energy profile (kcal/mol) illustrating the reaction pathways of the prenol radical in hydrogenation and α-C(sp³)–H functionalization with butanone; (c) proposed mechanism for the transfer hydrogenation of alkenes.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-6566230/v1/e79716863b05ebbc215666ec.png"},{"id":99676966,"identity":"de63038c-be11-4410-ad93-093154b6828c","added_by":"auto","created_at":"2026-01-07 08:10:31","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":783312,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6566230/v1/e4cdfbc4-d39c-4c04-8542-dd37c4d61376.pdf"},{"id":82672633,"identity":"2d910b04-ef93-4866-83c0-8e9c79cb495a","added_by":"auto","created_at":"2025-05-14 03:20:01","extension":"cif","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":645269,"visible":true,"origin":"","legend":"\u003cp\u003ecif file of compound 4a\u003c/p\u003e","description":"","filename":"4a.cif","url":"https://assets-eu.researchsquare.com/files/rs-6566230/v1/f44bcc14700c094366e56a37.cif"},{"id":82672638,"identity":"b90d9ef5-2b93-4fea-8383-5627a6a858ff","added_by":"auto","created_at":"2025-05-14 03:20:01","extension":"cif","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":437732,"visible":true,"origin":"","legend":"\u003cp\u003ecif file of compound 6m\u003c/p\u003e","description":"","filename":"6m.cif","url":"https://assets-eu.researchsquare.com/files/rs-6566230/v1/4b6a99bccd7867adeb7f8cf6.cif"},{"id":82672641,"identity":"46a22356-1893-4e55-8a9c-9ca4d514de47","added_by":"auto","created_at":"2025-05-14 03:20:01","extension":"cif","order_by":3,"title":"","display":"","copyAsset":false,"role":"supplement","size":892616,"visible":true,"origin":"","legend":"\u003cp\u003ecif file of compound 6a\u003c/p\u003e","description":"","filename":"6a.cif","url":"https://assets-eu.researchsquare.com/files/rs-6566230/v1/72e839d077eb125f6195422d.cif"},{"id":82673438,"identity":"30858a16-e425-4fe5-8645-e6a1d6be10dd","added_by":"auto","created_at":"2025-05-14 03:28:01","extension":"cif","order_by":4,"title":"","display":"","copyAsset":false,"role":"supplement","size":171607,"visible":true,"origin":"","legend":"\u003cp\u003ecif file of compound 7\u003c/p\u003e","description":"","filename":"7.cif","url":"https://assets-eu.researchsquare.com/files/rs-6566230/v1/d9da225b579b5dd99c869e34.cif"},{"id":82673648,"identity":"f7b2cdf5-2c6d-41e0-812f-a53a2348e7fd","added_by":"auto","created_at":"2025-05-14 03:36:01","extension":"cif","order_by":5,"title":"","display":"","copyAsset":false,"role":"supplement","size":1436094,"visible":true,"origin":"","legend":"cif file of compound 8","description":"","filename":"8.cif","url":"https://assets-eu.researchsquare.com/files/rs-6566230/v1/09815695eec5447a9a558902.cif"},{"id":82673437,"identity":"a0154efc-dea4-42d2-9d6b-05837a0e2e35","added_by":"auto","created_at":"2025-05-14 03:28:01","extension":"pdf","order_by":6,"title":"","display":"","copyAsset":false,"role":"supplement","size":8381889,"visible":true,"origin":"","legend":"Supporting Information","description":"","filename":"SupportingInformationPOMhydrogenationCWSorevised.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6566230/v1/5d2234184c7dfa8f8376fc11.pdf"},{"id":82672650,"identity":"23ae6351-cd0d-4af2-ae4b-44506e4783f1","added_by":"auto","created_at":"2025-05-14 03:20:02","extension":"docx","order_by":7,"title":"","display":"","copyAsset":false,"role":"supplement","size":1702441,"visible":true,"origin":"","legend":"","description":"","filename":"Tables.docx","url":"https://assets-eu.researchsquare.com/files/rs-6566230/v1/d28ed04f61ad2daf9852c477.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Decatungstate-Photocatalyzed Transfer Hydrogenation of Alkenes Using Alcohol as the Hydrogen Source","fulltext":[{"header":"Introduction","content":"\u003cp\u003eHydrogenation of alkenes is one of the most fundamental transformations in organic synthesis, typically requiring both a catalyst and a hydrogen source.\u003csup\u003e\u003cspan additionalcitationids=\"CR2 CR3 CR4 CR5 CR6 CR7 CR8 CR9 CR10 CR11 CR12 CR13 CR14 CR15 CR16 CR17 CR18\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e The most common hydrogen source is hydrogen gas (H₂), known for its 100% atom efficiency. However, safety concerns related to handling flammable and potentially explosive H₂ have led to the exploration of alternative hydrogen sources.\u003csup\u003e\u003cspan additionalcitationids=\"CR21 CR22 CR23 CR24 CR25 CR26 CR27 CR28 CR29 CR30 CR31 CR32 CR33 CR34 CR35 CR36 CR37\" citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003ePhotochemistry offers a novel approach for converting organic substrates into alternative hydrogen sources. One notable strategy involves photocatalytic reduction of alkenes to radical anions, which subsequently react with Br\u0026oslash;nsted-Lowry acids or solvents as proton donors to facilitate catalytic hydrogenation.\u003csup\u003e\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e For instance, Guo and Houk et al. employed the strong acid TfOH and thioxanthone (TX) to photo-catalytically reduce \u003cem\u003eα,β\u003c/em\u003e-unsaturated carbonyl compounds by using \u003cem\u003ep\u003c/em\u003e-xylene (solvent) as the proton source (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea).\u003csup\u003e\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u003c/sup\u003e Similarly, Polyzos et al. described an iridium-catalyzed reduction of alkenes, followed by a reaction with Br\u0026oslash;nsted-Lowry acids to produce alkanes (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb).\u003csup\u003e\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u003c/sup\u003e However, this technique is limited by the reduction potential of the targeted alkenes. An alternative strategy was then developed, where iridium complexes were usually used to photo-catalytically generate radical cations to undergo hydrogen atom transfer (HAT) reactions with alkenes to form hydrogen-adduct carbon radicals. This is followed by either protonation with a proton source or addition with a hydrogen radical source to achieve catalytic hydrogenation.\u003csup\u003e\u003cspan additionalcitationids=\"CR43 CR44 CR45\" citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e\u003c/sup\u003e For example, Wenger et al. demonstrated that an iridium photocatalyst mediated the HAT reaction between triethylamine (TEA) and alkenes, with subsequent radical addition completing alkene hydrogenation (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ec).\u003csup\u003e\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e\u003c/sup\u003e Moreover, Studer and coworkers developed an iridium-catalyzed system for generating phosphine radical cations that activated water molecules to form a PR₃\u0026ndash;H₂O radical cation intermediate, effectively utilizing both hydrogen atoms from H₂O in the alkene hydrogenation process through sequential heterolytic (H⁺) and homolytic (H\u0026bull;) O\u0026ndash;H bond cleavages (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed).\u003csup\u003e\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e\u003c/sup\u003e Despite these advancements, replacing these rare and costly iridium photocatalysts with more abundant and inexpensive alternatives would significantly enhance the sustainability of hydrogenation processes.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAlcohol is earth-abundant and sustainable, which would be a good candidate as a transfer hydrogenation reagent. However, the main difficulty for its use in the hydrogenation of alkenes originates from challenging homolytic cleavage of O\u0026ndash;H and α-C\u0026ndash;H bonds due to their high bond dissociation energies (BDE\u0026thinsp;=\u0026thinsp;\u003cem\u003eca\u003c/em\u003e 100 kcal/mol).\u003csup\u003e47\u003c/sup\u003e This is supported by currently reported photocatalysts, which solely mediate homolytic cleavage of the α-C\u0026ndash;H bond in alcohols, generating reactive nucleophilic α-C-centered radicals (\u0026bull;CR\u003csub\u003e2\u003c/sub\u003eOH) for conjugate additions with Michael acceptors (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e).\u003csup\u003e\u003cspan additionalcitationids=\"CR49 CR50 CR51 CR52\" citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e\u003c/sup\u003e We propose that if the homolytic cleavage of the α-C(sp\u0026sup3;)\u0026ndash;H bond of alcohol [R₂C(H)OH] generates a hydrogen radical (H\u0026bull;) and a relatively stable alcohol radical (\u0026bull;CR₂OH), this alcohol radical could undergo O\u0026ndash;H bond cleavage, rather than reacting with the alkene, producing a C\u0026thinsp;=\u0026thinsp;O double bond in aldehydes or ketones (R₂C\u0026thinsp;=\u0026thinsp;O) and a second H\u0026bull;. These two hydrogen radicals could readily add across the C\u0026thinsp;=\u0026thinsp;C double bond, enabling effective alkene hydrogenation (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eTransition metal-polyoxometalate hybrid clusters demonstrate good activity in mediating direct hydrogenation,\u003csup\u003e\u003cspan additionalcitationids=\"CR55\" citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e56\u003c/span\u003e\u003c/sup\u003e prompting us to explore whether an inexpensive and earth-abundant decatungstate anion, [W\u003csub\u003e10\u003c/sub\u003eO\u003csub\u003e32\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e alone can be used as a photocatalyst for transfer hydrogenation. Upon irradiation, the decatungstate anion is excited to a reactive state capable of abstracting α-H atoms from alcohols, generating alcohol radicals (\u0026bull;CR₂OH) and reduced decatungstate species, H\u003csup\u003e+\u003c/sup\u003e[W\u003csub\u003e10\u003c/sub\u003eO\u003csub\u003e32\u003c/sub\u003e]⁵\u003csup\u003e\u0026minus;\u003c/sup\u003e. The alcohol radical undergoes homolytic cleavage of the O\u0026ndash;H bond, forming an aldehyde or ketone and a hydrogen radical (H\u0026bull;). This hydrogen radical then reacts with the C\u0026thinsp;=\u0026thinsp;C double bond of an alkene (R₂C\u0026thinsp;=\u0026thinsp;CR₂), producing a carbon-centered radical (R₂(H)\u0026ndash;C(\u0026bull;)R₂). The photocatalytic cycle is completed when this alkyl radical undergoes HAT with H\u003csup\u003e+\u003c/sup\u003e[W\u003csub\u003e10\u003c/sub\u003eO\u003csub\u003e32\u003c/sub\u003e]⁵\u003csup\u003e\u0026minus;\u003c/sup\u003e, yielding the hydrogenated alkene [R₂(H)\u0026ndash;C(H)R₂] and regenerating the decatungstate anion [W\u003csub\u003e10\u003c/sub\u003eO\u003csub\u003e32\u003c/sub\u003e]⁴\u003csup\u003e\u0026minus;\u003c/sup\u003e. Herein, we report a simple, mild, and efficient strategy for alkene hydrogenation using alcohol as the hydrogen source and inexpensive decatungstate as the photocatalyst. To our knowledge, this study represents the first instance of using tungsten-based catalysts for the transfer hydrogenation of alkenes. Notably, the decatungstate/alcohol catalytic system exhibits excellent chemoselectivity, enabling selective hydrogenation of alkenes and alkynes even in the presence of reactive groups like ketones and carboxylic acids. These features highlight the significant potential of this approach for practical and sustainable applications in organic synthesis.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"Results","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\n \u003ch2\u003eCatalysis and Substrate Scope\u003c/h2\u003e\n \u003cp\u003eWe initially investigated prenol \u003cstrong\u003e2a\u003c/strong\u003e, a natural alcohol derived from biomass, as a hydrogen source for the transfer hydrogenation of 1,2-dibenzoylethylene (\u003cstrong\u003e1a\u003c/strong\u003e) (Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e). It is because the prenol-derived \u0026alpha;-C radical (Me₂C\u0026thinsp;=\u0026thinsp;C(H)CH(\u0026bull;)OH) formed during \u0026alpha;-C(sp\u0026sup3;)\u0026ndash;H bond activation can be stabilized by delocalization with the C\u0026thinsp;=\u0026thinsp;C double bond.\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e57\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e59\u003c/span\u003e\u003c/sup\u003e This stabilization likely reduces the reactivity of the radical toward \u003cstrong\u003e5a\u003c/strong\u003e, thereby enabling the homolytic cleavage of the O\u0026ndash;H bond to proceed efficiently. Upon 390 nm LED irradiation and with 5 mol% TBADT (tetrabutylammonium decatungstate) as the photocatalyst, the reaction yielded four types of products: the hydrogenated compound \u003cstrong\u003e4a\u003c/strong\u003e (Isolated yield: 86%), aldehyde \u003cstrong\u003e3a\u003c/strong\u003e, \u0026alpha;-C(sp\u0026sup3;)\u0026ndash;H bond addition compound \u003cstrong\u003e5a\u003c/strong\u003e (isolated yield: 5%), and a mixture of dimeric by-products arising from coupling of C\u0026thinsp;=\u0026thinsp;C double bond (Table S3 for their X-ray crystal structure). When TBADT was replaced with 2,4,6-triphenylpyrylium, a lower yield of compound \u003cstrong\u003e4a\u003c/strong\u003e was observed. In contrast, using anthraquinone as a photocatalyst led to the formation of compound \u003cstrong\u003e5a\u003c/strong\u003e (67%) as the major product. These findings speculate that the stability of the reduced photocatalyst, H\u003csup\u003e+\u003c/sup\u003e[photocatalyst]\u003csup\u003e\u0026ndash;\u003c/sup\u003e, plays a key role in determining whether the prenol-derived \u0026alpha;-C radical (Me\u003csub\u003e2\u003c/sub\u003eC\u0026thinsp;=\u0026thinsp;C(H)CH(\u0026bull;)OH) is capable of undergoing rearrangement to form \u003cstrong\u003e3a\u003c/strong\u003e and H\u0026bull; before the HAT step by H\u003csup\u003e+\u003c/sup\u003e[photocatalyst]\u003csup\u003e\u0026ndash;\u003c/sup\u003e occurs. The use of EosinY as a photocatalyst resulted in a mixture of dimeric by-products as major products, while \u003cstrong\u003e4a\u003c/strong\u003e and \u003cstrong\u003e5a\u003c/strong\u003e are minor products. EosinY was capable of photocatalytic C\u0026ndash;H bond addition of 2-benzylidenemalononitrile with simple alcohols in quantitative conversion.\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e49\u003c/span\u003e\u003c/sup\u003e As such, we replaced compound \u003cstrong\u003e1a\u003c/strong\u003e with 2-benzylidenemalononitrile, where EosinY catalyzed hydrogenation of 2-benzylidenemalononitrile with \u003cstrong\u003e2a\u003c/strong\u003e to form [PhC(H)\u003csub\u003e2\u003c/sub\u003eC(H)(CN)\u003csub\u003e2\u003c/sub\u003e] in 21% yield, along with a C\u0026ndash;H bond addition product in 73% yield (Scheme S1). This supports our abovementioned hypothesis that prenol-derived \u0026alpha;-C radical (Me₂C\u0026thinsp;=\u0026thinsp;C(H)CH(\u0026bull;)OH) has relatively higher stability, which allows hydrogenation to occur, even EosinY prefers to mediate C\u0026ndash;H bond addition.\u003c/p\u003e\n \u003cp\u003eNext, we evaluate the performance of primary and secondary alcohols in the TBADT-catalyzed transfer hydrogenation of 1,2-dibenzoylethylene (Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e). Prenol is the most effective, yielding \u003cstrong\u003e4a\u003c/strong\u003e with the highest isolated yield. Allyl alcohol (\u003cstrong\u003e2b\u003c/strong\u003e) also performed well, producing \u003cstrong\u003e4a\u003c/strong\u003e in 79% isolated yield, while natural alcohol geraniol (\u003cstrong\u003e2c\u003c/strong\u003e) afforded a comparable yield of 81%. Benzyl alcohol (\u003cstrong\u003e2d\u003c/strong\u003e) and pyridin-2-ylmethanol (\u003cstrong\u003e2e\u003c/strong\u003e) were efficient hydrogen donors, delivering isolated yields of 72% and 76%, respectively. Secondary alcohols such as 1-phenylethanol (\u003cstrong\u003e2f\u003c/strong\u003e) and 1-(pyridin-4-yl)ethan-1-ol (\u003cstrong\u003e2g\u003c/strong\u003e) achieved similarly high isolated yields (75% and 86%, respectively). Furan-2-ylmethanol (\u003cstrong\u003e2h\u003c/strong\u003e) is cumbersome in the catalysis based on the moderate isolated yield of \u003cstrong\u003e4a\u003c/strong\u003e (48%). Conversely, simple alcohols such as ethanol (\u003cstrong\u003e2i)\u003c/strong\u003e and 2-propanol (\u003cstrong\u003e2j)\u003c/strong\u003e produced lower isolated yields of \u003cstrong\u003e4a\u003c/strong\u003e (26% and 29%). These findings show that the nucleophilic alcohol \u0026alpha;-C-centered radicals (\u0026bull;CR\u003csub\u003e2\u003c/sub\u003eOH) contain an unsaturated moiety (R\u0026thinsp;=\u0026thinsp;benzene, pyridine or alkene), having high efficiency in the hydrogenation of alkene, probably due to the stabilization of the radical, allowing homolytic O\u0026ndash;H bond cleavage. Overall, these results demonstrate the feasibility of using a diverse array of primary and secondary alcohols as hydrogen sources in TBADT-mediated transfer hydrogenation, emphasizing the robustness and versatility of this approach.\u003c/p\u003e\n \u003cp\u003eWith optimized reaction conditions established, we explored the substrate scope of olefins, as summarized in Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e. The hydrogenation of 1,2-dibenzoylethylene (\u003cstrong\u003e1a\u003c/strong\u003e) with prenol produced \u003cstrong\u003e4a\u003c/strong\u003e in an excellent isolated yield (86%). Encouraged by this result, we explored \u0026alpha;,\u0026beta;-unsaturated carbonyl compounds. To our delight, the 4-phenyl-3-buten-2-one (\u003cstrong\u003e1b\u003c/strong\u003e) reacted efficiently to produce 4-phenylbutan-2-one (\u003cstrong\u003e4b\u003c/strong\u003e) in 76% isolated yield. Derivatives of \u003cstrong\u003e1b\u003c/strong\u003e with electron-donating and electron-withdrawing substituents at different positions \u003cem\u003eortho\u003c/em\u003e- (\u003cstrong\u003e1c\u003c/strong\u003e, \u003cem\u003eo\u003c/em\u003e-Me; \u003cstrong\u003e1d\u003c/strong\u003e, \u003cem\u003eo\u003c/em\u003e-F), \u003cem\u003emeta\u003c/em\u003e- (\u003cstrong\u003e1e\u003c/strong\u003e, \u003cem\u003em\u003c/em\u003e-OMe), and \u003cem\u003epara\u003c/em\u003e- (\u003cstrong\u003e1f\u003c/strong\u003e, \u003cem\u003ep\u003c/em\u003e-OMe; \u003cstrong\u003e1g\u003c/strong\u003e, \u003cem\u003ep\u003c/em\u003e-OH; \u003cstrong\u003e1h\u003c/strong\u003e, \u003cem\u003ep\u003c/em\u003e-Cl; \u003cstrong\u003e1i\u003c/strong\u003e, \u003cem\u003ep\u003c/em\u003e-F; \u003cstrong\u003e1j\u003c/strong\u003e, \u003cem\u003ep\u003c/em\u003e-CF\u003csub\u003e3\u003c/sub\u003e) were successfully hydrogenated, yielding the corresponding products (\u003cstrong\u003e4c\u003c/strong\u003e-\u003cstrong\u003e4j\u003c/strong\u003e) in moderate to high isolated yields (54\u0026ndash;85%). The results revealed that the electron-rich substituents at the \u0026beta; position (\u003cstrong\u003e1c\u003c/strong\u003e, \u003cstrong\u003e1e, 1f, 1g\u003c/strong\u003e) led to slightly reduced isolated yields (54\u0026ndash;63%). Replacing the phenyl group with a methyl (\u003cstrong\u003e1k\u003c/strong\u003e) or \u003cem\u003e\u0026alpha;\u003c/em\u003e-naphthyl substituent (\u003cstrong\u003e1l\u003c/strong\u003e) did not significantly affect product yields, producing \u003cstrong\u003e4k\u003c/strong\u003e and \u003cstrong\u003e4l\u003c/strong\u003e in 66% and 71% isolated yields, respectively. However, the hydrogenation of \u003cstrong\u003e1m\u003c/strong\u003e, which contains a pyridine substituent, led to reductive coupling instead of hydrogenation to form \u003cstrong\u003e6m\u003c/strong\u003e in 91% isolated yield. Moreover, 1-phenylbuten-1-one (\u003cstrong\u003e1n\u003c/strong\u003e) and 1,3-diphenylpropen-1-one (\u003cstrong\u003e1o\u003c/strong\u003e) were hydrogenated, giving a moderate isolated yield of 41% and 32%, respectively. Carboxylic acid and ester substituents enhanced reactivity, yielding \u003cstrong\u003e4p\u003c/strong\u003e-\u003cstrong\u003e4s\u003c/strong\u003e in 67\u0026ndash;87% isolated yields. Terminal olefins, namely 3-buten-2-one (\u003cstrong\u003e1t\u003c/strong\u003e) and 1-phenylprop-2-en-1-one (\u003cstrong\u003e1u\u003c/strong\u003e) were effectively hydrogenated leading to \u003cstrong\u003e4t\u003c/strong\u003e (86%) and \u003cstrong\u003e4u\u003c/strong\u003e (84%) in good isolated yields, respectively. When more substituted terminal olefin, namely, 3-methylbut-3-en-2-one (\u003cstrong\u003e1v\u003c/strong\u003e) was hydrogenated, the isolated yield of \u003cstrong\u003e4v\u003c/strong\u003e dropped to 64%. Cycloenone \u003cstrong\u003e1w\u003c/strong\u003e and more substituted derivative \u003cstrong\u003e1x\u003c/strong\u003e also reacted to form cyclohexanones \u003cstrong\u003e4w\u003c/strong\u003e (76%) and \u003cstrong\u003e4x\u003c/strong\u003e (43%), respectively. Next, reactive functional groups namely ester, nitro, and cyano groups in \u003cstrong\u003e1y\u003c/strong\u003e\u0026ndash;\u003cstrong\u003e1ab\u003c/strong\u003e were well compatible in catalysis (38\u0026ndash;46%). Pyridine substituent promoted the hydrogenation, where 1,2-di(4-pyridyl)ethylene (\u003cstrong\u003e1ac\u003c/strong\u003e) was converted into \u003cstrong\u003e4ac\u003c/strong\u003e with an excellent isolated yield of 94%. Remarkably, the anti-lymphoma and leukemia cancer drug, namely Ibrutinib (\u003cstrong\u003e1ad\u003c/strong\u003e) was hydrogenated to produce \u003cstrong\u003e4ad\u003c/strong\u003e in 56% isolated yield, demonstrating the utility of this catalytic method in the late-stage functionalization of pharmaceutical agents.\u003c/p\u003e\n \u003cp\u003eSubsequently, the hydrogenation of other types of unsaturated bonds were tested. N\u0026thinsp;=\u0026thinsp;N double bonds (\u003cstrong\u003e1ae)\u003c/strong\u003e were efficiently reduced under optimized conditions, yielding \u003cstrong\u003e4ae\u003c/strong\u003e in 86%. It appears that the N lone pair of electrons does not affect the reaction mechanism. Phenylacetylene and its derivatives with various substituents (\u003cstrong\u003e9a\u003c/strong\u003e-\u003cstrong\u003e9h\u003c/strong\u003e) were efficiently converted to the corresponding terminal olefins (\u003cstrong\u003e10a\u003c/strong\u003e-\u003cstrong\u003e10h\u003c/strong\u003e) in 64\u0026ndash;91% isolated yields. Alkynes with carbonyl groups underwent double hydrogenation to directly form alkanes (\u003cstrong\u003e4a\u003c/strong\u003e-\u003cstrong\u003e4u\u003c/strong\u003e, 69\u0026ndash;83%), indicating that the carbonyl groups facilitate hydrogenation.\u003c/p\u003e\n\u003c/div\u003e\n\u003ch3\u003eMechanistic Investigations\u003c/h3\u003e\n\u003cp\u003eTo clarify the catalytic mechanism, deuterated benzyl alcohols PhCH\u003csub\u003e2\u003c/sub\u003eOD and PhCD\u003csub\u003e2\u003c/sub\u003eOH were reacted with \u003cstrong\u003e1ac\u003c/strong\u003e (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ea). These reactions resulted in a 1:1 molar ratio of \u003cstrong\u003e4ac-\u003c/strong\u003e\u003cstrong\u003ed\u003c/strong\u003e and \u003cstrong\u003e3d\u003c/strong\u003e, and a 1:1 molar ratio of \u003cstrong\u003e4ac-\u003c/strong\u003e\u003cstrong\u003ed\u003c/strong\u003e and \u003cstrong\u003e3d-\u003c/strong\u003e\u003cstrong\u003ed\u003c/strong\u003e, respectively (Figure S4 and S5), confirming that alcohols are the sole hydrogen source. Moreover, introducing the radical scavenger TEMPO (1 equiv.) significantly inhibited the formation of \u003cstrong\u003e4ac\u003c/strong\u003e as the H\u0026bull; and alcohol \u0026alpha;-C centered radicals were quenched by TEMPO (Figure S7 and S8 showing the presence of the quenched radicals in HRMS). These findings indicate that the mechanism involves the activation of the \u0026alpha;-C(sp\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e)\u0026ndash;H bond of alcohols to form alcohol \u0026alpha;-C-centered radicals in the first step. To further understand why the alcohol \u0026alpha;-C-centered radical undergoes O-H bond cleavage rather than directly adding to the alkene during catalysis, density functional theory (DFT) calculations were performed using butenone \u003cstrong\u003e1t\u003c/strong\u003e and prenol \u0026alpha;-C-centered radical \u003cstrong\u003eR2a\u003c/strong\u003e as model substrates (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003eb). Two potential hydrogenation pathways were explored. In \u003cstrong\u003ePath I\u003c/strong\u003e, the \u003cstrong\u003eR2a\u003c/strong\u003e undergoes homolytic cleavage of its O\u0026ndash;H bond and addition of H\u0026bull; at the \u003cem\u003e\u0026beta;\u003c/em\u003e-position of \u003cstrong\u003e1t\u003c/strong\u003e via \u003cstrong\u003eTS-A\u003c/strong\u003e (\u0026Delta;G\u0026thinsp;=\u0026thinsp;23.3 kcal/mol) to form thermodynamic intermediates \u003cstrong\u003eA\u003c/strong\u003e and \u003cstrong\u003e3a\u003c/strong\u003e (\u0026Delta;G = -8.3 kcal/mol). In contrast, the addition of H\u0026bull; at the \u003cem\u003e\u0026alpha;\u003c/em\u003e-position of \u003cstrong\u003e1t\u003c/strong\u003e is infeasible due to the high kinetic barrier (\u003cstrong\u003ePath II\u003c/strong\u003e, TS-B: \u0026Delta;G\u0026thinsp;=\u0026thinsp;43.8 kcal/mol). In the C\u0026ndash;C bond formation pathway (\u003cstrong\u003ePath III\u003c/strong\u003e), \u003cstrong\u003eR2a\u003c/strong\u003e adds to \u003cstrong\u003e1t\u003c/strong\u003e via \u003cstrong\u003eTS-C\u003c/strong\u003e (\u0026Delta;G\u0026thinsp;=\u0026thinsp;13.6 kcal/mol), forming kinetic intermediate \u003cstrong\u003eC\u003c/strong\u003e (\u0026Delta;G = -5.8 kcal/mol). Based on \u003cstrong\u003eTS-A\u003c/strong\u003e and \u003cstrong\u003eTS-C\u003c/strong\u003e, both \u003cstrong\u003ePath I\u003c/strong\u003e and \u003cstrong\u003ePath III\u003c/strong\u003e are viable at room temperature, but hydrogenation is more favorable due to the thermodynamic intermediates \u003cstrong\u003eA\u003c/strong\u003e and \u003cstrong\u003e3a\u003c/strong\u003e. It is consistent with experimental observations, where decatungstate-photocatalyzed hydrogenation of butenone with prenol requires prolonged reaction times at room temperature (\u0026gt;\u0026thinsp;12 hours), but proceeds significantly faster at higher temperatures (70\u0026deg;C, 6 hours). As shown in Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ea, TBADT and 2,4,6-triphenylpyrylium selectively catalyze hydrogenation, while anthraquinone promotes C\u0026ndash;H bond addition. These results indicate that the reduced photocatalyst H\u003csup\u003e+\u003c/sup\u003e[W\u003csub\u003e10\u003c/sub\u003eO\u003csub\u003e32\u003c/sub\u003e]\u003csup\u003e5\u0026minus;\u003c/sup\u003e, which is formed by the \u0026alpha;-C(sp\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e)\u0026ndash;H bond activation of alcohols, favors \u003cstrong\u003ePath I\u003c/strong\u003e to complete the catalysis.\u003c/p\u003e\n\u003cp\u003eBased on the experimental data and DFT calculations, a plausible mechanism for decatungstate-photocatalyzed transfer hydrogenation of alkenes using alcohol as the hydrogen source is proposed (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ec). Upon 390 nm LED light irradiation, decatungstate transitions to an excited state and rapidly relaxes to its reactive state \u003cstrong\u003ew\u003c/strong\u003e\u003cstrong\u003eO\u003c/strong\u003e. This \u003cstrong\u003ew\u003c/strong\u003e\u003cstrong\u003eO\u003c/strong\u003e species initiates the process by transferring a hydrogen atom to produce a carbon-centered alcohol radical, \u0026bull;CROH (\u003cstrong\u003eI\u003c/strong\u003e).\u003csup\u003e\u003cspan class=\"CitationRef\"\u003e60\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e62\u003c/span\u003e\u003c/sup\u003e The resulting radical undergoes first hydrogen atom transfer (\u003cstrong\u003ePath I\u003c/strong\u003e) to alkene, forming a radical intermediate \u003cstrong\u003eIII\u003c/strong\u003e and aldehyde/ketone (\u003cstrong\u003eII\u003c/strong\u003e). The intermediate \u003cstrong\u003eIII\u003c/strong\u003e subsequently undergoes a second HAT with H\u003csup\u003e+\u003c/sup\u003e[W\u003csub\u003e10\u003c/sub\u003eO\u003csub\u003e32\u003c/sub\u003e]\u003csup\u003e5\u0026minus;\u003c/sup\u003e, producing the final alkane product (\u003cstrong\u003eIV\u003c/strong\u003e) and regenerating the starting catalyst [W\u003csub\u003e10\u003c/sub\u003eO\u003csub\u003e32\u003c/sub\u003e]\u003csup\u003e4\u0026minus;\u003c/sup\u003e to close the catalytic cycle. In addition, the alcohol radical \u0026bull;CROH (\u003cstrong\u003eI\u003c/strong\u003e) can undergo conjugate addition with alkenes via \u003cstrong\u003ePath III\u003c/strong\u003e to generate intermediate \u003cstrong\u003eV\u003c/strong\u003e, which reacts with H\u003csup\u003e+\u003c/sup\u003e[W\u003csub\u003e10\u003c/sub\u003eO\u003csub\u003e32\u003c/sub\u003e]\u003csup\u003e5\u0026minus;\u003c/sup\u003e to yield a byproduct \u003cstrong\u003eVI\u003c/strong\u003e.\u003c/p\u003e\n\u003cp\u003eIn summary, we have developed a simple, mild, and efficient photocatalytic method for the transfer hydrogenation of alkenes using alcohols as the hydrogen source and inexpensive decatungstate as the photocatalyst. This method demonstrates broad substrate compatibility, high chemoselectivity, and practicality under ambient conditions. Mechanistic studies reveal that the hydrogenation proceeds via a radical-mediated pathway involving the sequential homolytic cleavage of \u0026alpha;-C(sp\u0026sup3;)\u0026ndash;H and O\u0026ndash;H bonds in alcohols. DFT calculations further confirmed that the hydrogenation pathway is more exothermic than the side \u0026alpha;-C(sp\u0026sup3;)\u0026ndash;H functionalization route, indicating it is thermodynamically favored, consistent with experimental observations. These findings highlight the significant potential of the decatungstate/alcohol catalytic system in practical organic synthesis, offering a sustainable approach for alkene hydrogenation.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003eFor the detailed experimental methods described in this manuscript, please refer to the Supplementary Information.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eData Availability\u003c/h2\u003e\n\u003cp\u003eCCDC-2384191 (for \u003cstrong\u003e6m\u003c/strong\u003e), 2384192 (for \u003cstrong\u003e4a\u003c/strong\u003e), and 2402528-2402530 (for \u003cstrong\u003e6a, 7\u0026nbsp;\u003c/strong\u003eand\u003cstrong\u003e\u0026nbsp;8\u003c/strong\u003e), contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: + 44 1223 336033.\u003c/p\u003e\n\u003ch2\u003eCompeting interests\u003c/h2\u003e \u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e \u003ch2\u003eSupplementary Information\u003c/h2\u003e \u003cp\u003eExperimental procedures and supporting data (mechanistic studies, DFT calculations, compound characterization data, and NMR spectra) can be found in the Supporting Information.\u003c/p\u003e \u003ch2\u003eAuthor contributions\u003c/h2\u003e \u003cp\u003eT. Z., Y. R. Chi, L. Wu, and C.-W. S. conceived and designed the project. T. Z., X. L., and S.-Y. L. performed and analyzed the chemical experiments. Z.-F. Z. and M.-D. S. performed and analyzed the DFT calculations. T. Z., L. Wu, and C.-W. S. analyzed the data and prepared the manuscript. All the authors reviewed the manuscript.\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e \u003cp\u003eThis work is supported by the Ministry of Education Singapore, AcRF Tier 2 (MOE2019-T2-2-129) and A*STAR MTC Individual Research Grants (M21K2c0117) for the financial support.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eVerendel JJ, P\u0026agrave;mies O, Di\u0026eacute;guez M, Andersson PG (2014) Asymmetric Hydrogenation of Olefins Using Chiral Crabtree-type Catalysts: Scope and Limitations. Chem Rev 114:2130\u0026ndash;2169\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWang D-S, Chen Q-A, Lu S-M, Zhou Y-G (2012) Asymmetric Hydrogenation of Heteroarenes and Arenes. Chem Rev 112:2557\u0026ndash;2590\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eQu R, Junge K, Beller M (2023) Hydrogenation of Carboxylic Acids, Esters, and Related Compounds over Heterogeneous Catalysts: A Step toward Sustainable and Carbon-Neutral Processes. Chem Rev 123:1103\u0026ndash;1165\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eCabr\u0026eacute; A, Verdaguer X, Riera A (2022) Recent Advances in the Enantioselective Synthesis of Chiral Amines via Transition Metal-Catalyzed Asymmetric Hydrogenation. Chem Rev 122:269\u0026ndash;339\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWen J, Wang F, Zhang X (2021) Asymmetric Hydrogenation Catalyzed by First-row Transition Metal Complexes. Chem Soc Rev 50:3211\u0026ndash;3237\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eL\u0026uuml;ckemeier L, Pierau M, Glorius F (2023) Asymmetric arene hydrogenation: towards sustainability and application. Chem Soc Rev 52:4996\u0026ndash;5012\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKumar A, Daw P, Milstein D (2022) Homogeneous Catalysis for Sustainable Energy: Hydrogen and Methanol Economies, Fuels from Biomass, and Related Topics. Chem Rev 122:385\u0026ndash;441\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLam J, Szkop K, Mosaferi E, Stephan DW (2019) FLP Catalysis: Main Group Hydrogenations of Organic Unsaturated Substrates. Chem Soc Rev 48:3592\u0026ndash;3612\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKraft S, Ryan K, Kargbo RB (2017) Recent Advances in Asymmetric Hydrogenation of Tetrasubstituted Olefins. J Am Chem Soc 139:11630\u0026ndash;11641\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDing Z, Luo Y, Yuan Q, Wang G, Yu Z, Zhao M, Liu D, Zhang W (2024) Ru-Catalyzed Asymmetric Hydrogenation of α,β-Unsaturated γ-Lactams. \u003cem\u003eJ. Am. Chem. Soc.\u003c/em\u003e 146, 25312\u0026thinsp;\u0026ndash;\u0026thinsp;25320\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eFriedfeld MR, Zhong H, Ruck RT, Shevlin M, Chirik PJ (2018) Cobalt-catalyzed asymmetric hydrogenation of enamides enabled by single-electron reduction. \u003cem\u003eScience\u003c/em\u003e 360, 888\u0026thinsp;\u0026ndash;\u0026thinsp;893\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMargarita C, Andersson PG (2017) Evolution and Prospects of the Asymmetric Hydrogenation of Unfunctionalized Olefins. J Am Chem Soc 139:1346\u0026ndash;1356\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDavies AT, Pickett PM, Slawin AMZ, Smith AD (2014) Asymmetric Synthesis of Tri- and Tetrasubstituted Trifluoromethyl Dihydropyranones from α\u0026ndash;Aroyloxyaldehydes via NHC Redox Catalysis. \u003cem\u003eACS Catal.\u003c/em\u003e 4, 2696\u0026thinsp;\u0026ndash;\u0026thinsp;2700\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKim AN, Stoltz BM (2020) Recent Advances in Homogeneous Catalysts for the Asymmetric Hydrogenation of Heteroarenes. ACS Catal 10:13834\u0026ndash;13851\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWei H, Luo Y, Li J, Chen J, Gridnev ID, Zhang W (2025) Enantioselective Synthesis of Chiral β\u003csup\u003e2\u003c/sup\u003e\u0026ndash;Amino Phosphorus Derivatives via Nickel-Catalyzed Asymmetric Hydrogenation. J Am Chem Soc 147:342\u0026ndash;352\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMas-Rosellό J, Smejkal T, Cramer N (2020) Iridium-catalyzed acid-assisted asymmetric hydrogenation of oximes to hydroxylamines. \u003cem\u003eScience\u003c/em\u003e 368, 1098\u0026thinsp;\u0026ndash;\u0026thinsp;1102\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eYang F, Xie J-H, Zhou Q-L (2023) Highly Efficient Asymmetric Hydrogenation Catalyzed by Iridium Complexes with Tridentate Chiral Spiro Aminophosphine Ligands. Acc Chem Res 56:332\u0026ndash;349\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eChakrabortty S, Konieczny K, de Zwart FJ, Bobylev EO, Bar\u0026aacute;th E, Tin S, M\u0026uuml;ller BH, Reek JNH, de Bruin B, de Vries JG (2023) Cobalt-Catalyzed Enantioselective Hydrogenation of Trisubstituted Carbocyclic Olefins: An Access to Chiral Cyclic Amides. Angew Chem Int Ed 62:e202301329\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWiesenfeldt MP, Nairoukh Z, Li W, Glorius F (2017) Hydrogenation of Fluoroarenes: Direct Access to All-cis-(multi)-fluorinated Cycloalkanes. Science 357:908\u0026ndash;912\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWang D, Astruc D (2015) The Golden Age of Transfer Hydrogenation. Chem Rev 115:6621\u0026ndash;6686\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSantana CG, Krische MJ (2021) From Hydrogenation to Transfer Hydrogenation to Hydrogen Auto-Transfer in Enantioselective Metal-Catalyzed Carbonyl Reductive Coupling: Past, Present, and Future. ACS Catal 11:5572\u0026ndash;5585\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePang M, Chen J-Y, Zhang S, Liao R-Z, Tung C-H, Wang W (2020) Controlled Partial Transfer Hydrogenation of Quinolines by Cobalt-Amido Cooperative Catalysis. Nat Commun 11:1249\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLau S, Gasperini D, Webster RL (2021) Amine-Boranes as Transfer Hydrogenation and Hydrogenation Reagents: A Mechanistic Perspective. Angew Chem Int Ed 60:14272\u0026ndash;14294\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhou Q, Meng W, Yang J, Du HA (2018) Continuously Regenerable Chiral Ammonia Borane for Asymmetric Transfer Hydrogenations. Angew Chem Int Ed 57:12111\u0026ndash;12115\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eCummings SP, Le T-N, Fernandez GE, Quiambao LG, Stokes BJ (2016) Tetrahydroxydiboron-Mediated Palladium-Catalyzed Transfer Hydrogenation and Deuteriation of Alkenes and Alkynes Using Water as the Stoichiometric H or D Atom Donor. J Am Chem Soc 138:6107\u0026ndash;6110\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eXu H, Yang P, Chuanprasit P, Hirao H, Zhou JS (2015) Nickel-Catalyzed asymmetric transfer hydrogenation of hydrazones and other ketimines. Angew Chem Int Ed 54:5112\u0026ndash;5116\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhao E, Li M, Xu B, Wang X-L, Jing Y, Ma D, Mitchell S, P\u0026eacute;rez-Ram\u0026iacute;rez J, Chen Z (2022) Transfer Hydrogenation with a Carbon-Nitride-Supported Palladium Single-Atom Photocatalyst and Water as a Proton Source. Angew Chem Int Ed 61:e202207410\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSun Y, Wang C, Yang P, Yue J-Y, Xu C, Zhou JS, Tang B (2023) Hydrogen bond enhanced enantioselectivity in the Nickel-catalyzed transfer hydrogenation of α-substituted acrylic acid with formic acid. ACS Catal 13:14213\u0026ndash;14220\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBroggi J, Jurč\u0026iacute;k V, Songis O, Poater A, Cavallo L, Slawin AMZ, Cazin CS (2013) J. The Isolation of [Pd{OC(O)H}(H)(NHC)(PR\u003csub\u003e3\u003c/sub\u003e)] (NHC\u0026thinsp;=\u0026thinsp;N-Heterocyclic Carbene) and Its Role in Alkene and Alkyne Reductions Using Formic Acid. J Am Chem Soc 135:4588\u0026ndash;4591\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWang F, Yang T, Wu T, Zheng L-S, Yin C, Shi Y, Ye X-Y, Chen G-Q, Zhang X (2021) Asymmetric Transfer Hydrogenation of α\u0026ndash;Substituted-β-Keto Carbonitriles via Dynamic Kinetic Resolution. J Am Chem Soc 143:2477\u0026ndash;2483\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLin Y, Xu G, Tang W (2024) Chiral Polymeric Diamine Ligands for Iridium-Catalyzed Asymmetric Transfer Hydrogenation. J Am Chem Soc 146:27736\u0026ndash;27744\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWu J, Chen Z, Barnard JH, Gunasekar R, Pu C, Wu X, Zhang S, Ruan J, Xiao J (2022) Synthesis of Chiral Piperidines from Pyridinium Salts via Rhodium-Catalysed Transfer Hydrogenation. Nat Catal 5:982\u0026ndash;992\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLan S, Huang H, Liu W, Xu C, Lei X, Dong W, Liu J, Yang S, Cotman AE, Zhang Q, Fang X (2024) Asymmetric Transfer Hydrogenation of Cyclobutenediones. J Am Chem Soc 146:4942\u0026ndash;4957\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKattamuri PV, West JG (2020) Hydrogenation of Alkenes via Cooperative Hydrogen Atom Transfer. J Am Chem Soc 142:19316\u0026ndash;19326\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLiu X, Huang L, Ma Y, She G, Zhou P, Zhu L, Zhang Z (2024) Enable Biomass-Derived Alcohols Mediated Alkylation and Transfer Hydrogenation. Nat Commun 15:7012\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLuo G-G, Pan Z-H, Han B-L, Dong G-L, Deng C-L, Azam M, Tao Y-W, He J, Sun C-F, Sun D (2023) Total Structure, Electronic Structure and Catalytic Hydrogenation Activity of Metal-Deficient Chiral Polyhydride Cu57 Nanoclusters. Angew Chem Int Ed 62:e202306849\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eQian L, Yu C, Gan L, Tang X, Wang Y, Liu G, Leng X, Sun Z, Guo Y, Xue X-S, Huang Z (2024) Iridium-Catalyzed Enantioselective Transfer Hydrogenation of 1,1-Dialkylethenes with Ethanol: Scope and Mechanism. J Am Chem Soc 146:3427\u0026ndash;3437\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZuo W, Lough AJ, Li YF, Morris RH (2013) Amine(imine)diphosphine Iron Catalysts for Asymmetric Transfer Hydrogenation of Ketones and Imines. Science 342:1080\u0026ndash;1083\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePac C, Ihama M, Yasuda M, Miyauchi Y, Sakurai H (1981) Tris(2,2'-Bipyridine)Ruthenium(2+)-Mediated Photoreduction of Olefins with 1-Benzyl-1,4-Dihydronicotinamide: a Mechanistic Probe for Electron-Transfer Reactions of NAD(P)H-Model Compounds. J Am Chem Soc 103:6495\u0026ndash;6497\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKang W-J, Li B, Duan M, Pan G, Sun W, Ding A, Zhang Y, Houk KN, Guo H (2022) Discovery of a Thioxanthone-TfOH Complex as a Photoredox Catalyst for Hydrogenation of Alkenes Using p-Xylene as both Electron and Hydrogen Sources. Angew Chem Int Ed 61:e202211562\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eCzyz ML, Taylor MS, Horngren TH, Polyzos A (2021) Reductive Activation and Hydrofunctionalization of Olefins by Multiphoton Tandem Photoredox Catalysis. ACS Catal 11:5472\u0026ndash;5480\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLarionova NA, Ondozabal JM, Cambeiro XC (2021) Reduction of Electron-Deficient Alkenes Enabled by a Photoinduced Hydrogen Atom Transfer. Adv Synth Catal 363:558\u0026ndash;564\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePark Y, Tian L, Kim S, Pabst TP, Kim J, Scholes GD, Chirik PJ (2022) Visible-Light-Driven, Iridium-Catalyzed Hydrogen Atom Transfer: Mechanistic Studies, Identification of Intermediates, and Catalyst Improvements. JACS Au 2:407\u0026ndash;418\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhou W, Dmitriev IA, Melchiorre P (2023) Reductive Cross-Coupling of Olefins via a Radical Pathway. J Am Chem Soc 145:25098\u0026ndash;25102\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSchreier MR, Pfund B, Guo X, Wenger OS (2020) Phototriggered hydrogen atom transfer from an iridium hydride complex to unactivated olefins. Chem Sci 11:8582\u0026ndash;8594\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhang J, M\u0026uuml;ck-Lichtenfeld C, Studer A (2023) Photocatalytic Phosphine-Mediated Water Activation for Radical Hydrogenation. Nature 619:506\u0026ndash;513\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLuo YR (2007) Comprehensive Handbook of Chemical Bond Energies. CRC, Boca Raton, FL\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJeffrey JL, Terrett JA, MacMillan DWC (2015) O-H Hydrogen Bonding Promotes H-Atom Transfer from C\u0026thinsp;\u0026ndash;\u0026thinsp;H Bonds for C-Alkylation of Alcohols. Science 349:1532\u0026ndash;1536\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eFan X, Rong J, Wu H, Zhou Q, Deng H, Tan J, Da, Xue C, Wu L, Tao H, Wu J (2018) Eosin Y as a Direct Hydrogen-Atom Transfer Photocatalyst for the Functionalization of C\u0026thinsp;\u0026ndash;\u0026thinsp;H Bonds. Angew Chem Int Ed 57:8514\u0026ndash;8518\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLiu L, Liu J, Liang X-A, Wang S, Lei A (2019) Visible Light-Induced Direct α-C\u0026thinsp;\u0026ndash;\u0026thinsp;H Functionalization of Alcohols. Nat Commun 10:467\u0026ndash;453\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePaul S, Filippini D, Ficarra F, Melnychenko H, Janot C, Silvi M (2023) Oxetane Synthesis via Alcohol C\u0026thinsp;\u0026ndash;\u0026thinsp;H Functionalization. J Am Chem Soc 145:15688\u0026ndash;15694\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eTwilton J, Christensen M, DiRocco DA, Ruck RT, Davies IW, MacMillan DWC (2018) Selective Hydrogen Atom Abstraction through Induced Bond Polarization: Direct α-Arylation of Alcohols through Photoredox, HAT, and Nickel Catalysis. Angew Chem Int Ed 57:5369\u0026ndash;5373\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eCapaldo L, Merli D, Fagnoni M, Ravelli D (2019) Visible Light Uranyl Photocatalysis: Direct C\u0026thinsp;\u0026ndash;\u0026thinsp;H to C\u0026thinsp;\u0026ndash;\u0026thinsp;C Bond Conversion. ACS Catal 9:3054\u0026ndash;3058\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWang S-S, Yang G-Y (2015) Recent Advances in Polyoxometalate-Catalyzed Reactions. Chem Rev 115:4893\u0026ndash;4962\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZhang M, Li Z, Feng Y, Xin X, Yang G-Y, Lv H (2023) Highly Selective Hydrogenolysis of Lignin Β-O-4 Models by A Coupled Polyoxometalate/Cds Photocatalytic System. Green Chem 25:10091\u0026ndash;10100\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLi S, Ma Y, Zhao Y, Liu R, Zhao Y, Dai X, Ma N, Streb C, Chen X (2023) Hydrogenation Catalysis by Hydrogen Spillover on Platinum-Functionalized Heterogeneous Boronic Acid-Polyoxometalates. Angew Chem Int Ed 62:e202314999\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGobbi A, Frenking G (1994) Resonance Stabilization in Allyl Cation, Radical, and Anion. J Am Chem Soc 116:9275\u0026ndash;9286\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMo Y, Lin Z, Wu W, Zhang Q (1996) Delocalization in Allyl Cation, Radical, and Anion. J Phys Chem 100:6469\u0026ndash;6474\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHioe J, Zipse H (2010) Radical Stability and Its Role in Synthesis and Catalysis. Org Biomol Chem 8:3609\u0026ndash;3617\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eTanielian C, Decatungstate, Photocatalysis (1998) \u003cem\u003eCoord. Chem. Rev.\u003c/em\u003e 178\u0026thinsp;\u0026ndash;\u0026thinsp;180, 1165\u0026thinsp;\u0026ndash;\u0026thinsp;1181\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLaudadio G, Deng Y, van der Wal K, Ravelli D, Nun\u0026otilde; M, Fagnoni M, Guthrie D, Sun Y, No\u0026euml;l T (2020) C(sp\u003csup\u003e3\u003c/sup\u003e)-H Functionalizations of Light Hydrocarbons Using Decatungstate Photocatalysis in Flow. Science 369:92\u0026ndash;96\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eRavelli D, Fagnoni M, Fukuyama T, Nishikawa T, Ryu I (2018) Site-Selective C\u0026thinsp;\u0026ndash;\u0026thinsp;H Functionalization by Decatungstate Anion Photocatalysis: Synergistic Control by Polar and Steric Effects Expands the Reaction Scope. ACS Catal 8:701\u0026ndash;713\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Tables","content":"\u003cp\u003eTables 1 and 2 are available in the Supplementary Files section.\u003c/p\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-6566230/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6566230/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eWe present a simple and efficient photocatalytic method for the transfer hydrogenation of alkenes and alkynes using alcohol as the hydrogen source and inexpensive decatungstate as the photocatalyst. Our approach operates under mild, ambient conditions and demonstrates broad substrate compatibility, accommodating alkyl, aryl, and heteroatom-substituted alkenes and alkynes. To our knowledge, this study represents the first instance of using tungsten-based catalysts for the transfer hydrogenation of alkenes. Notably, the decatungstate/alcohol catalytic system exhibits excellent chemoselectivity, enabling selective hydrogenation of alkenes and alkynes even in the presence of reactive groups like ketones and carboxylic acids. These features highlight the considerable potential of this approach for practical and sustainable applications in organic synthesis.\u003c/p\u003e","manuscriptTitle":"Decatungstate-Photocatalyzed Transfer Hydrogenation of Alkenes Using Alcohol as the Hydrogen Source","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-05-14 03:19:56","doi":"10.21203/rs.3.rs-6566230/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"c636e144-0d13-4371-8345-329eb28c752c","owner":[],"postedDate":"May 14th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":48413591,"name":"Physical sciences/Chemistry/Catalysis/Photocatalysis"},{"id":48413592,"name":"Physical sciences/Chemistry/Chemical synthesis/Synthetic chemistry methodology"}],"tags":[],"updatedAt":"2026-01-07T08:10:22+00:00","versionOfRecord":{"articleIdentity":"rs-6566230","link":"https://doi.org/10.1038/s41467-025-67482-1","journal":{"identity":"nature-communications","isVorOnly":false,"title":"Nature Communications"},"publishedOn":"2026-01-06 05:00:00","publishedOnDateReadable":"January 6th, 2026"},"versionCreatedAt":"2025-05-14 03:19:56","video":"","vorDoi":"10.1038/s41467-025-67482-1","vorDoiUrl":"https://doi.org/10.1038/s41467-025-67482-1","workflowStages":[]},"version":"v1","identity":"rs-6566230","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6566230","identity":"rs-6566230","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}