{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,13]],"date-time":"2026-10-13T02:39:40Z","timestamp":1791859180158,"version":"4.3.4"},"reference-count":38,"publisher":"Springer Science and Business Media LLC","issue":"1","license":[{"start":{"date-parts":[[2024,7,23]],"date-time":"2024-07-23T00:00:00Z","timestamp":1721692800000},"content-version":"tdm","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0"},{"start":{"date-parts":[[2024,7,23]],"date-time":"2024-07-23T00:00:00Z","timestamp":1721692800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0"}],"funder":[{"DOI":"10.13039\/501100002920","name":"Research Grants Council, University Grants Committee","doi-asserted-by":"publisher","award":["16305523"],"award-info":[{"award-number":["16305523"]}],"id":[{"id":"10.13039\/501100002920","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100011002","name":"National Science Foundation of China | National Natural Science Foundation of China-Yunnan Joint Fund","doi-asserted-by":"publisher","award":["21825101"],"award-info":[{"award-number":["21825101"]}],"id":[{"id":"10.13039\/501100011002","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["link.springer.com"],"crossmark-restriction":false},"short-container-title":["Nat Commun"],"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Cleavage of carbon-carbon bonds remains a challenging task in organic synthesis. Traditional methods for splitting C<jats:sub>sp2<\/jats:sub>=C<jats:sub>sp2<\/jats:sub> bonds into two halves typically involve non-redox (metathesis) or oxidative (ozonolysis) mechanisms, limiting their synthetic potential. Disproportionative deconstruction of alkenes, which yields one reduced and one oxidized fragment, remains an unexplored area. In this study, we introduce a redox-neutral approach for deleting a C<jats:sub>sp2<\/jats:sub> carbon unit from substituted arylalkenes, resulting in the formation of an arene (reduction) and a carbonyl product (oxidation). This transformation is believed to proceed through a mechanistic sequence involving visible-light-promoted anti-Markovnikov hydration, followed by photoredox cleavage of C<jats:sub>sp3<\/jats:sub>-C<jats:sub>sp3<\/jats:sub> bond in the alcohol intermediate. A crucial consideration in this design is addressing the compatibility between the highly reactive oxy radical species in the latter step and the required hydrogen-atom-transfer (HAT) reagent for both steps. We found that ethyl thioglycolate serves as the optimal hydrogen-atom shuttle, offering remarkable chemoselectivity among multiple potential HAT events in this transformation. By using D<jats:sub>2<\/jats:sub>O, we successfully prepared dideuteromethylated (-CD<jats:sub>2<\/jats:sub>H) arenes with good heavy atom enrichment. This work presents a redox-neutral alternative for alkene deconstruction, with considerable potential in late-stage modification of complex molecules.<\/jats:p>","DOI":"10.1038\/s41467-024-50624-2","type":"journal-article","created":{"date-parts":[[2024,7,23]],"date-time":"2024-07-23T22:49:40Z","timestamp":1721774980000},"update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Water mediated redox-neutral cleavage of arylalkenes via photoredox catalysis"],"prefix":"10.1038","volume":"15","author":[{"given":"Ke","family":"Liao","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuqi","family":"Fang","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lei","family":"Sheng","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0703-5831","authenticated-orcid":false,"given":"Jiean","family":"Chen","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8377-8923","authenticated-orcid":false,"given":"Yong","family":"Huang","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"297","published-online":{"date-parts":[[2024,7,23]]},"reference":[{"key":"50624_CR1","doi-asserted-by":"publisher","first-page":"2411","DOI":"10.1021\/cr050989d","volume":"107","author":"A Corma","year":"2007","unstructured":"Corma, A., Iborra, S. & Velty, A. Chemical routes for the transformation of biomass into chemicals. Chem. Rev. 107, 2411\u20132502 (2007).","journal-title":"Chem. Rev."},{"key":"50624_CR2","doi-asserted-by":"publisher","first-page":"41","DOI":"10.1002\/anie.198800411","volume":"27","author":"H Baumann","year":"1988","unstructured":"Baumann, H. et al. Natural fats and oils-renewable raw materials for the chemical industry. Angew. Chem. Int. Ed. 27, 41\u201362 (1988).","journal-title":"Angew. Chem. Int. Ed."},{"key":"50624_CR3","doi-asserted-by":"publisher","first-page":"2981","DOI":"10.1021\/cr100371y","volume":"111","author":"RI McDonald","year":"2011","unstructured":"McDonald, R. I., Liu, G. & Stahl, S. S. Palladium(II)-catalyzed alkene functionalization via nucleopalladation: stereochemical pathways and enantioselective catalytic applications. Chem. Rev. 111, 2981\u20133019 (2011).","journal-title":"Chem. Rev."},{"key":"50624_CR4","doi-asserted-by":"publisher","first-page":"9816","DOI":"10.1021\/acs.chemrev.6b00005","volume":"116","author":"R Remy","year":"2016","unstructured":"Remy, R. & Bochet, C. G. Arene-alkene cycloaddition. Chem. Rev. 116, 9816\u20139849 (2016).","journal-title":"Chem. Rev."},{"key":"50624_CR5","doi-asserted-by":"publisher","first-page":"14754","DOI":"10.1021\/acscatal.2c04964","volume":"12","author":"Z Zeng","year":"2022","unstructured":"Zeng, Z., Gao, H., Zhou, Z. & Yi, W. Intermolecular redox-neutral carboamination of C-C multiple bonds initiated by transition-metal-catalyzed C-H activation. ACS Catal. 12, 14754\u201314772 (2022).","journal-title":"ACS Catal."},{"key":"50624_CR6","doi-asserted-by":"publisher","first-page":"8912","DOI":"10.1021\/acs.chemrev.6b00334","volume":"116","author":"SW Crossley","year":"2016","unstructured":"Crossley, S. W., Obradors, C., Martinez, R. M. & Shenvi, R. A. Mn-, Fe-, and Co-catalyzed radical hydrofunctionalizations of olefins. Chem. Rev. 116, 8912\u20139000 (2016).","journal-title":"Chem. Rev."},{"key":"50624_CR7","doi-asserted-by":"publisher","first-page":"14649","DOI":"10.1021\/acs.chemrev.1c00620","volume":"121","author":"JL Kennemur","year":"2021","unstructured":"Kennemur, J. L., Maji, R., Scharf, M. J. & List, B. Catalytic asymmetric hydroalkoxylation of C-C multiple bonds. Chem. Rev. 121, 14649\u201314681 (2021).","journal-title":"Chem. Rev."},{"key":"50624_CR8","doi-asserted-by":"publisher","first-page":"8731","DOI":"10.1021\/acscatal.3c01221","volume":"13","author":"S Zhang","year":"2023","unstructured":"Zhang, S. & Findlater, M. Electrochemically driven hydrogen atom transfer catalysis: A tool for Csp3\/Si-H functionalization and hydrofunctionalization of alkenes. ACS Catal. 13, 8731\u20138751 (2023).","journal-title":"ACS Catal."},{"key":"50624_CR9","doi-asserted-by":"publisher","first-page":"11222","DOI":"10.1002\/anie.201209833","volume":"52","author":"MA Drahl","year":"2013","unstructured":"Drahl, M. A., Manpadi, M. & Williams, L. J. C-C fragmentation: origins and recent applications. Angew. Chem. Int. Ed. 52, 11222\u201311251 (2013).","journal-title":"Angew. Chem. Int. Ed."},{"key":"50624_CR10","doi-asserted-by":"publisher","first-page":"243","DOI":"10.1038\/nature06351","volume":"450","author":"AH Hoveyda","year":"2007","unstructured":"Hoveyda, A. H. & Zhugralin, A. R. The remarkable metal-catalysed olefin metathesis reaction. Nature 450, 243\u2013251 (2007).","journal-title":"Nature"},{"key":"50624_CR11","doi-asserted-by":"publisher","first-page":"380","DOI":"10.1038\/nature20800","volume":"541","author":"X Shen","year":"2017","unstructured":"Shen, X. et al. Kinetically E-selective macrocyclic ring-closing metathesis. Nature 541, 380\u2013385 (2017).","journal-title":"Nature"},{"key":"50624_CR12","doi-asserted-by":"publisher","first-page":"925","DOI":"10.1021\/cr50023a005","volume":"58","author":"PS Bailey","year":"2002","unstructured":"Bailey, P. S. The reactions of ozone with organic compounds. Chem. Rev. 58, 925\u20131010 (2002).","journal-title":"Chem. Rev."},{"key":"50624_CR13","doi-asserted-by":"publisher","first-page":"15138","DOI":"10.1002\/anie.202014974","volume":"60","author":"Z Hassan","year":"2021","unstructured":"Hassan, Z., Stahlberger, M., Rosenbaum, N. & Brase, S. Criegee intermediates beyond ozonolysis: Synthetic and mechanistic insights. Angew. Chem. Int. Ed. 60, 15138\u201315152 (2021).","journal-title":"Angew. Chem. Int. Ed."},{"key":"50624_CR14","doi-asserted-by":"publisher","first-page":"4233","DOI":"10.1016\/j.tet.2017.03.039","volume":"73","author":"TJ Fisher","year":"2017","unstructured":"Fisher, T. J. & Dussault, P. H. Alkene ozonolysis. Tetrahedron 73, 4233\u20134258 (2017).","journal-title":"Tetrahedron"},{"key":"50624_CR15","doi-asserted-by":"publisher","first-page":"3824","DOI":"10.1021\/ja017295g","volume":"124","author":"BR Travis","year":"2002","unstructured":"Travis, B. R., Narayan, R. S. & Borhan, B. Osmium tetroxide-promoted catalytic oxidative cleavage of olefins: An organometallic ozonolysis. J. Am. Chem. Soc. 124, 3824\u20133825 (2002).","journal-title":"J. Am. Chem. Soc."},{"key":"50624_CR16","first-page":"478","volume":"33","author":"R Pappo","year":"1955","unstructured":"Pappo, R., Allen, D. S., Lemieux, R. U. & Johnson, W. S. Osmium tetroxide-catalyzed periodate oxidation of olefinic bonds. Can. J. Chem. 33, 478\u2013479 (1955).","journal-title":"Can. J. Chem."},{"key":"50624_CR17","doi-asserted-by":"publisher","first-page":"1552","DOI":"10.1021\/ol100290a","volume":"12","author":"KC Nicolaou","year":"2010","unstructured":"Nicolaou, K. C., Adsool, V. A. & Hale, C. R. H. An expedient procedure for the oxidative cleavage of olefinic bonds with PhI(OAc)2, NMO, and catalytic OsO4. Org. Lett. 12, 1552\u20131555 (2010).","journal-title":"Org. Lett."},{"key":"50624_CR18","doi-asserted-by":"publisher","first-page":"3050","DOI":"10.1021\/acscatal.6b03654","volume":"7","author":"G Urgoitia","year":"2017","unstructured":"Urgoitia, G., SanMartin, R., Herrero, M. T. & Dom\u00ednguez, E. Aerobic cleavage of alkenes and alkynes into carbonyl and carboxyl compounds. ACS Catal. 7, 3050\u20133060 (2017).","journal-title":"ACS Catal."},{"key":"50624_CR19","doi-asserted-by":"publisher","first-page":"2092","DOI":"10.1002\/asia.201600671","volume":"11","author":"JP Wan","year":"2016","unstructured":"Wan, J. P., Gao, Y. & Wei, L. Recent advances in transition-metal-free oxygenation of alkene C=C double bonds for carbonyl generation. Chem. Asian J. 11, 2092\u20132102 (2016).","journal-title":"Chem. Asian J."},{"key":"50624_CR20","doi-asserted-by":"publisher","first-page":"485","DOI":"10.1021\/acs.chemrev.0c00335","volume":"121","author":"SH Shi","year":"2021","unstructured":"Shi, S. H., Liang, Y. & Jiao, N. Electrochemical oxidation induced selective C-C bond cleavage. Chem. Rev. 121, 485\u2013505 (2021).","journal-title":"Chem. Rev."},{"key":"50624_CR21","doi-asserted-by":"publisher","first-page":"12313","DOI":"10.1021\/acs.chemrev.3c00219","volume":"123","author":"YF Liang","year":"2023","unstructured":"Liang, Y. F. et al. Carbon-carbon bond cleavage for late-stage functionalization. Chem. Rev. 123, 12313\u201312370 (2023).","journal-title":"Chem. Rev."},{"key":"50624_CR22","doi-asserted-by":"publisher","first-page":"832","DOI":"10.1002\/anie.201607948","volume":"56","author":"Y Deng","year":"2017","unstructured":"Deng, Y. et al. Disulfide-catalyzed visible-light-mediated oxidative cleavage of C=C bonds and evidence of an olefin\u2212disulfide charge-transfer complex. Angew. Chem. Int. Ed. 56, 832\u2013836 (2017).","journal-title":"Angew. Chem. Int. Ed."},{"key":"50624_CR23","doi-asserted-by":"publisher","first-page":"81","DOI":"10.1038\/s41586-022-05211-0","volume":"610","author":"A Ruffoni","year":"2022","unstructured":"Ruffoni, A., Hampton, C., Simonetti, M. & Leonori, D. Photoexcited nitroarenes for the oxidative cleavage of alkenes. Nature 610, 81\u201386 (2022).","journal-title":"Nature"},{"key":"50624_CR24","doi-asserted-by":"publisher","first-page":"15437","DOI":"10.1021\/jacs.2c05648","volume":"144","author":"DE Wise","year":"2022","unstructured":"Wise, D. E. et al. Photoinduced oxygen transfer using nitroarenes for the anaerobic cleavage of alkenes. J. Am. Chem. Soc. 144, 15437\u201315442 (2022).","journal-title":"J. Am. Chem. Soc."},{"key":"50624_CR25","doi-asserted-by":"publisher","first-page":"1997","DOI":"10.1021\/acs.accounts.6b00304","volume":"49","author":"KA Margrey","year":"2016","unstructured":"Margrey, K. A. & Nicewicz, D. A. A general approach to catalytic alkene anti-Markovnikov hydrofunctionalization reactions via acridinium photoredox catalysis. Acc. Chem. Res. 49, 1997\u20132006 (2016).","journal-title":"Acc. Chem. Res."},{"key":"50624_CR26","doi-asserted-by":"publisher","first-page":"1432","DOI":"10.1021\/acscatal.6b03388","volume":"7","author":"X Hu","year":"2017","unstructured":"Hu, X., Zhang, G., Bu, F. & Lei, A. Visible-light-mediated anti-Markovnikov hydration of olefins. ACS Catal. 7, 1432\u20131437 (2017).","journal-title":"ACS Catal."},{"key":"50624_CR27","doi-asserted-by":"publisher","first-page":"100763","DOI":"10.1016\/j.xcrp.2022.100763","volume":"3","author":"K Liao","year":"2022","unstructured":"Liao, K., Wu, F., Chen, J. & Huang, Y. Catalytic cleavage and functionalization of bulky and inert Csp3-Csp3 bonds via a relayed proton-coupled electron transfer strategy. Cell Rep. Phys. Sci. 3, 100763 (2022).","journal-title":"Cell Rep. Phys. Sci."},{"key":"50624_CR28","doi-asserted-by":"publisher","first-page":"12284","DOI":"10.1021\/jacs.3c02745","volume":"145","author":"K Liao","year":"2023","unstructured":"Liao, K. et al. Photoredox cleavage of a Csp3-Csp3 bond in aromatic hydrocarbons. J. Am. Chem. Soc. 145, 12284\u201312292 (2023).","journal-title":"J. Am. Chem. Soc."},{"key":"50624_CR29","doi-asserted-by":"publisher","first-page":"4099","DOI":"10.1039\/D3CS00023K","volume":"52","author":"J Zhang","year":"2023","unstructured":"Zhang, J. & Rueping, M. Metallaphotoredox catalysis for sp3 C-H functionalizations through hydrogen atom transfer (HAT). Chem. Soc. Rev. 52, 4099\u20134120 (2023).","journal-title":"Chem. Soc. Rev."},{"key":"50624_CR30","doi-asserted-by":"publisher","first-page":"2429","DOI":"10.1021\/acs.chemrev.1c00256","volume":"122","author":"L Chang","year":"2022","unstructured":"Chang, L., An, Q., Duan, L., Feng, K. & Zuo, Z. Alkoxy radicals see the light: New paradigms of photochemical synthesis. Chem. Rev. 122, 2429\u20132486 (2022).","journal-title":"Chem. Rev."},{"key":"50624_CR31","doi-asserted-by":"publisher","first-page":"1600","DOI":"10.1021\/ja038656q","volume":"126","author":"S Fukuzumi","year":"2004","unstructured":"Fukuzumi, S. et al. Electron transfer state of 9-mesityl-10-methylacridinium ion with a much longer lifetime and higher energy than that of the natural photosynthetic reaction center. J. Am. Chem. Soc. 126, 1600\u20131601 (2004).","journal-title":"J. Am. Chem. Soc."},{"key":"50624_CR32","doi-asserted-by":"publisher","first-page":"1326","DOI":"10.1126\/science.aac9895","volume":"349","author":"NA Romero","year":"2015","unstructured":"Romero, N. A., Margrey, K. A., Tay, N. E. & Nicewicz, D. A. Site-selective arene C-H amination via photoredox catalysis. Science 349, 1326\u20131330 (2015).","journal-title":"Science"},{"key":"50624_CR33","doi-asserted-by":"publisher","first-page":"6896","DOI":"10.1002\/anie.201702940","volume":"56","author":"L Wang","year":"2017","unstructured":"Wang, L., Wu, F., Chen, J., Nicewicz, D. A. & Huang, Y. Visible-light-mediated [4+2] cycloaddition of styrenes: Synthesis of tetralin derivatives. Angew. Chem. Int. Ed. 56, 6896\u20136900 (2017).","journal-title":"Angew. Chem. Int. Ed."},{"key":"50624_CR34","doi-asserted-by":"publisher","first-page":"13652","DOI":"10.1021\/jacs.7b08086","volume":"139","author":"L Pitzer","year":"2017","unstructured":"Pitzer, L., Sandfort, F., Strieth-Kalthoff, F. & Glorius, F. Intermolecular radical addition to carbonyls enabled by visible light photoredox initiated hole catalysis. J. Am. Chem. Soc. 139, 13652\u201313655 (2017).","journal-title":"J. Am. Chem. Soc."},{"key":"50624_CR35","doi-asserted-by":"publisher","first-page":"6634","DOI":"10.1021\/acs.chemrev.1c00795","volume":"122","author":"S Kopf","year":"2022","unstructured":"Kopf, S. et al. Recent developments for the deuterium and tritium labeling of organic molecules. Chem. Rev. 122, 6634\u20136718 (2022).","journal-title":"Chem. Rev."},{"key":"50624_CR36","doi-asserted-by":"publisher","first-page":"4336","DOI":"10.1063\/1.443567","volume":"76","author":"D Cavagnat","year":"1982","unstructured":"Cavagnat, D. & Lascombe, J. Effect of the internal rotation of the CHD2 group on the aliphatic CH stretching mode of the toluenes C6H5CHD2 and C6D5CHD2 in solid crystalline phases. J. Chem. Phys. 76, 4336\u20134348 (1982).","journal-title":"J. Chem. Phys."},{"key":"50624_CR37","doi-asserted-by":"publisher","first-page":"243","DOI":"10.1021\/ar980014y","volume":"33","author":"E Baciocchi","year":"2000","unstructured":"Baciocchi, E., Bietti, M. & Lanzalunga, O. Mechanistic aspects of \u03b2-bond-cleavage reactions of aromatic radical cations. Acc. Chem. Res. 33, 243\u2013251 (2000).","journal-title":"Acc. Chem. Res."},{"key":"50624_CR38","doi-asserted-by":"publisher","first-page":"1785","DOI":"10.1002\/(SICI)1521-3765(19990604)5:6<1785::AID-CHEM1785>3.0.CO;2-0","volume":"5","author":"E Baciocchi","year":"1999","unstructured":"Baciocchi, E., Bietti, M. & Steenken, S. Kinetic and product studies on the side-chain fragmentation of 1-arylalkanol radical cations in aqueous solution: Oxygen versus carbon acidity. Chem. Eur. J. 5, 1785\u20131793 (1999).","journal-title":"Chem. Eur. J."}],"container-title":["Nature Communications"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.nature.com\/articles\/s41467-024-50624-2.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/www.nature.com\/articles\/s41467-024-50624-2","content-type":"text\/html","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/www.nature.com\/articles\/s41467-024-50624-2.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2024,7,23]],"date-time":"2024-07-23T22:49:46Z","timestamp":1721774986000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.nature.com\/articles\/s41467-024-50624-2"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,7,23]]},"references-count":38,"journal-issue":{"issue":"1","published-online":{"date-parts":[[2024,12]]}},"alternative-id":["50624"],"URL":"https:\/\/doi.org\/10.1038\/s41467-024-50624-2","relation":{},"ISSN":["2041-1723"],"issn-type":[{"value":"2041-1723","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,7,23]]},"assertion":[{"value":"25 March 2024","order":1,"name":"received","label":"Received","group":{"name":"ArticleHistory","label":"Article History"}},{"value":"16 July 2024","order":2,"name":"accepted","label":"Accepted","group":{"name":"ArticleHistory","label":"Article History"}},{"value":"23 July 2024","order":3,"name":"first_online","label":"First Online","group":{"name":"ArticleHistory","label":"Article History"}},{"value":"The authors declare no competing interests.","order":1,"name":"Ethics","group":{"name":"EthicsHeading","label":"Competing interests"}}],"article-number":"6227"}}