{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,2]],"date-time":"2026-10-02T13:55:40Z","timestamp":1790949340965,"version":"4.1.0"},"reference-count":40,"publisher":"American Chemical Society (ACS)","issue":"39","license":[{"start":{"date-parts":[[2026,9,18]],"date-time":"2026-09-18T00:00:00Z","timestamp":1789689600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,9,18]],"date-time":"2026-09-18T00:00:00Z","timestamp":1789689600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,9,18]],"date-time":"2026-09-18T00:00:00Z","timestamp":1789689600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/501100006769","name":"Russian Science Foundation","doi-asserted-by":"publisher","award":["25-43-02058"],"award-info":[{"award-number":["25-43-02058"]}],"id":[{"id":"10.13039\/501100006769","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,10,2]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Palladium(II) complexes of the TPA family (TPA = tris(2-pyridylmethyl)amine) catalyze selective C(sp3)\u2013H oxyfunctionalizations but have so far been unable to activate \u201cgreen\u201d oxidant H2O2, instead requiring peroxycarboxylic acids (2\u20134 equiv, best results coming with m-CPBA). Herein, we show that hydrogen peroxide itself, conveniently delivered as its solid surrogates (UHP and SPC), can serve as the terminal oxidant in Pd(TPA)-catalyzed nondirected C(sp3)\u2013H oxygenation, with carboxylic acid anhydrides as cocatalytic H2O2 activators. Depending on the conditions, alcohols or ketones form, with the catalyst sustaining up to 1.6 \u00d7 104 turnovers. The protocol is applied to the selective oxidation of complex natural products (steroids and terpenoids).<\/jats:p>","DOI":"10.1021\/acs.orglett.6c03151","type":"journal-article","created":{"date-parts":[[2026,9,18]],"date-time":"2026-09-18T22:01:22Z","timestamp":1789768882000},"page":"12207-12211","source":"Crossref","is-referenced-by-count":0,"title":["Nondirected Palladium-Catalyzed C(sp3)\u2013H\nOxygenation with H2O2"],"prefix":"10.1021","volume":"28","author":[{"given":"Dmitry P.","family":"Lubov","sequence":"first","affiliation":[{"name":"Zelinsky Institute of Organic Chemistry RAS , Leninsky Pr. 47 , ,","place":["Moscow, Russia, 119991"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Elizaveta M.","family":"Zhernikova","sequence":"additional","affiliation":[{"name":"Zelinsky Institute of Organic Chemistry RAS , Leninsky Pr. 47 , ,","place":["Moscow, Russia, 119991"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7009-8950","authenticated-orcid":true,"given":"Konstantin P.","family":"Bryliakov","sequence":"additional","affiliation":[{"name":"Zelinsky Institute of Organic Chemistry RAS , Leninsky Pr. 47 , ,","place":["Moscow, Russia, 119991"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,18]]},"reference":[{"key":"2026100208364458900_cit1","doi-asserted-by":"publisher","first-page":"1869","DOI":"10.1039\/C4CY00087K","article-title":"Recent\nDevelopments in Liquid-Phase Selective Oxidation Using Environmentally\nBenign Oxidants and Mesoporous Metal Silicates","volume":"4","author":"Kholdeeva","year":"2014","journal-title":"Catal. Sci. Technol."},{"key":"2026100208364458900_cit2","doi-asserted-by":"crossref","first-page":"127","DOI":"10.1007\/3418_2011_3","article-title":"Liquid-Phase Selective\nOxidation by Multimetallic Active Sites of Polyoxometalate-Based Molecular\nCatalysts","volume-title":"Bifunctional Molecular Catalysis","author":"Mizuno","year":"2011"},{"key":"2026100208364458900_cit3","doi-asserted-by":"crossref","DOI":"10.1093\/oso\/9780198506980.001.0001","volume-title":"Green Chemistry: Theory\nand Practice","author":"Anastas","year":"2000"},{"key":"2026100208364458900_cit4","doi-asserted-by":"publisher","first-page":"1437","DOI":"10.1039\/C1CS15219J","article-title":"Fundamentals\nof Green Chemistry: Efficiency in Reaction Design","volume":"41","author":"Sheldon","year":"2012","journal-title":"Chem. Soc. Rev."},{"key":"2026100208364458900_cit5","doi-asserted-by":"publisher","first-page":"3352","DOI":"10.1039\/b803584a","article-title":"E Factors,\nGreen Chemistry and Catalysis: An Odyssey","author":"Sheldon","year":"2008","journal-title":"Chem.\nCommun."},{"key":"2026100208364458900_cit6","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1002\/9781118356760.ch1","article-title":"Environmentally\nBenign Oxidants","volume-title":"Liquid Phase Oxidation\nvia Heterogeneous Catalysis","author":"Strukul","year":"2013"},{"key":"2026100208364458900_cit7","doi-asserted-by":"publisher","first-page":"11406","DOI":"10.1021\/acs.chemrev.7b00167","article-title":"Catalytic\nAsymmetric Oxygenations with the Environmentally Benign Oxidants H2O2 and O2","volume":"117","author":"Bryliakov","year":"2017","journal-title":"Chem.\nRev."},{"key":"2026100208364458900_cit8","doi-asserted-by":"publisher","first-page":"217108","DOI":"10.1016\/j.ccr.2025.217108","article-title":"Heterolytic Activation of Hydrogen Peroxide and Selective\nOxidations with d0-Heterometallic Polyoxometalates: Recent\nAdvances and Mechanistic Insights","volume":"547","author":"Maksimchuk","year":"2026","journal-title":"Coord. Chem.\nRev."},{"key":"2026100208364458900_cit9","doi-asserted-by":"crossref","DOI":"10.1007\/978-981-32-9751-7","volume-title":"Frontiers of Green\nCatalytic Selective Oxidations","author":"Bryliakov","year":"2019"},{"key":"2026100208364458900_cit10","doi-asserted-by":"publisher","first-page":"659","DOI":"10.1021\/jo01062a004","article-title":"Reactions\nof Hydrogen Peroxide. VII.\nAlkali-Catalyzed Epoxidation and Oxidation Using a Nitrile as Co-Reactant","volume":"26","author":"Payne","year":"1961","journal-title":"J. Org. Chem."},{"key":"2026100208364458900_cit11","doi-asserted-by":"publisher","first-page":"888","DOI":"10.1021\/jo00154a031","article-title":"Epoxidation of Alkenes\nwith Trichloroacetonitrile\/Hydrogen Peroxide in a Neutral Biphasic\nSolvent System","volume":"48","author":"Arias","year":"1983","journal-title":"J. Org. Chem."},{"key":"2026100208364458900_cit12","doi-asserted-by":"publisher","first-page":"8161","DOI":"10.1021\/ja403491j","article-title":"Catalytic\nAsymmetric Oxidation of\nN-Sulfonyl Imines with Hydrogen Peroxide\u2013Trichloroacetonitrile\nSystem","volume":"135","author":"Uraguchi","year":"2013","journal-title":"J. Am. Chem. Soc."},{"key":"2026100208364458900_cit13","doi-asserted-by":"publisher","first-page":"2299","DOI":"10.1016\/S0040-4039(00)00165-9","article-title":"A Practical,\nEfficient, and Rapid\nMethod for the Oxidation of Electron Deficient Pyridines Using Trifluoroacetic\nAnhydride and Hydrogen Peroxide\u2013Urea Complex","volume":"41","author":"Caron","year":"2000","journal-title":"Tetrahedron Lett."},{"key":"2026100208364458900_cit14","doi-asserted-by":"publisher","first-page":"0933","DOI":"10.1055\/s-2002-31903","article-title":"Selective Oxidation\nof N-Alkyl Imines\nto Oxaziridines Using UHP\/Maleic Anhydride System","volume":"2002","author":"Damavandi","year":"2002","journal-title":"Synlett"},{"key":"2026100208364458900_cit15","doi-asserted-by":"publisher","first-page":"9165","DOI":"10.1039\/D0RA00265H","article-title":"Recyclable\nAnhydride Catalyst for H2O2 Oxidation: N-Oxidation\nof Pyridine Derivatives","volume":"10","author":"Gajeles","year":"2020","journal-title":"RSC Adv."},{"key":"2026100208364458900_cit16","doi-asserted-by":"publisher","first-page":"31657","DOI":"10.1039\/D4RA05962J","article-title":"Maleic\nAnhydride Derivatives as Catalysts\nfor N-Oxidation of Pyridine Using Hydrogen Peroxide","volume":"14","author":"Gajeles","year":"2024","journal-title":"RSC Adv."},{"key":"2026100208364458900_cit17","doi-asserted-by":"publisher","first-page":"73","DOI":"10.1016\/S1381-1169(00)00433-7","article-title":"Asymmetric\nMn(III)-Salen Catalyzed Epoxidation of Unfunctionalized Alkenes with\nin Situ Generated Peroxycarboxylic Acids","volume":"165","author":"Pietika\u0308inen","year":"2001","journal-title":"J.\nMol. Catal. A: Chem."},{"key":"2026100208364458900_cit18","doi-asserted-by":"publisher","first-page":"2231","DOI":"10.1055\/s-0037-1609446","article-title":"An Efficient\nOxidation of Sulfides\nto Sulfones with Urea\u2013Hydrogen Peroxide in the Presence of\nPhthalic Anhydride in Ethyl Acetate","volume":"50","author":"Lutz","year":"2018","journal-title":"Synthesis"},{"key":"2026100208364458900_cit19","doi-asserted-by":"publisher","first-page":"4015","DOI":"10.1016\/0040-4039(95)00702-E","article-title":"Epoxidation of Olefins\nwith Formamide\u2013Hydrogen\nPeroxide","volume":"36","author":"Chen","year":"1995","journal-title":"Tetrahedron Lett."},{"key":"2026100208364458900_cit20","doi-asserted-by":"publisher","first-page":"2569","DOI":"10.1021\/jo01328a052","article-title":"Epoxidation of Alkenes\nwith O-Ethylperoxycarbonic Acid Generated in Situ in an Alkaline Biphasic\nSolvent System","volume":"44","author":"Bach","year":"1979","journal-title":"J. Org. Chem."},{"key":"2026100208364458900_cit21","doi-asserted-by":"publisher","first-page":"1087","DOI":"10.1021\/cs3002226","article-title":"Oxidation\nof Alkenes with H2O2 by an in-Situ Prepared\nMn(II)\/Pyridine-2-carboxylic Acid Catalyst and the Role of Ketones\nin Activating H2O2","volume":"2","author":"Dong","year":"2012","journal-title":"ACS\nCatal."},{"key":"2026100208364458900_cit22","doi-asserted-by":"publisher","first-page":"3486","DOI":"10.1021\/acscatal.6b00320","article-title":"Mechanism of Alkene,\nAlkane, and Alcohol Oxidation with H2O2 by an\nin Situ Prepared MnII\/Pyridine-2-carboxylic Acid Catalyst","volume":"6","author":"Saisaha","year":"2016","journal-title":"ACS Catal."},{"key":"2026100208364458900_cit23","doi-asserted-by":"publisher","first-page":"6504","DOI":"10.1021\/ol503410e","article-title":"Chemoselective Hydroxylation of Aliphatic\nsp3 C\u2013H Bonds Using a Ketone Catalyst and Aqueous\nH2O2","volume":"16","author":"Pierce","year":"2014","journal-title":"Org. Lett."},{"key":"2026100208364458900_cit24","doi-asserted-by":"publisher","first-page":"3826","DOI":"10.1021\/acs.orglett.6b01832","article-title":"An Iminium Salt\nOrganocatalyst for Selective Aliphatic C\u2013H Hydroxylation","volume":"18","author":"Wang","year":"2016","journal-title":"Org. Lett."},{"key":"2026100208364458900_cit25","doi-asserted-by":"publisher","first-page":"4302","DOI":"10.1021\/acscatal.2c00392","article-title":"Amine Organocatalysis\nof Remote, Chemoselective C(sp3)\u2013H Hydroxylation","volume":"12","author":"Hahn","year":"2022","journal-title":"ACS Catal."},{"key":"2026100208364458900_cit26","doi-asserted-by":"publisher","first-page":"11150","DOI":"10.1039\/D0DT02247K","article-title":"Palladium\nAminopyridine Complexes Catalyzed Selective\nBenzylic C\u2013H Oxidations with Peracetic Acid","volume":"49","author":"Lubov","year":"2020","journal-title":"Dalton Trans."},{"key":"2026100208364458900_cit27","doi-asserted-by":"publisher","first-page":"1359","DOI":"10.1021\/acs.orglett.2c04371","article-title":"A Predictably\nSelective Palladium-Catalyzed Aliphatic C\u2013H Oxygenation","volume":"25","author":"Lubov","year":"2023","journal-title":"Org. Lett."},{"key":"2026100208364458900_cit28","doi-asserted-by":"publisher","first-page":"115563","DOI":"10.1016\/j.jcat.2024.115563","article-title":"Palladium\nCatalyzed C(sp3)\u2013H Trifluoroethoxylation","volume":"435","author":"Lubov","year":"2024","journal-title":"J. Catal."},{"key":"2026100208364458900_cit29","doi-asserted-by":"publisher","first-page":"116895","DOI":"10.1016\/j.jcat.2026.116895","article-title":"Palladium\nCatalyzed Selective Benzylic C\u2013H Alkoxylation","volume":"459","author":"Lubov","year":"2026","journal-title":"J. Catal."},{"key":"2026100208364458900_cit30","doi-asserted-by":"publisher","first-page":"13632","DOI":"10.1021\/jacs.5b08719","article-title":"Catalytic Role of\nMultinuclear Palladium\u2013Oxygen Intermediates in Aerobic Oxidation\nFollowed by Hydrogen Peroxide Disproportionation","volume":"137","author":"Ingram","year":"2015","journal-title":"J. Am. Chem. Soc."},{"key":"2026100208364458900_cit31","doi-asserted-by":"publisher","first-page":"25948","DOI":"10.1021\/jacs.3c09340","article-title":"Ligand-Enabled \u03b3-C(sp3)\u2013H\nHydroxylation of Free Amines with Aqueous Hydrogen Peroxide","volume":"145","author":"Li","year":"2023","journal-title":"J. Am. Chem. Soc."},{"key":"2026100208364458900_cit32","doi-asserted-by":"publisher","first-page":"4848","DOI":"10.1021\/acscatal.2c00879","article-title":"Roles of\nLigand and Oxidant in Pd(II)-Catalyzed and Ligand-Enabled C(sp3)\u2013H Lactonization in Aliphatic Carboxylic Acid: Mechanistic\nStudies","volume":"12","author":"Xu","year":"2022","journal-title":"ACS Catal."},{"key":"2026100208364458900_cit33","doi-asserted-by":"publisher","first-page":"1325","DOI":"10.1055\/s-1995-4128","article-title":"Sodium Perborate\nand Sodium Percarbonate in Organic Synthesis","volume":"1995","author":"Muzart","year":"1995","journal-title":"Synthesis"},{"key":"2026100208364458900_cit34","doi-asserted-by":"publisher","first-page":"6145","DOI":"10.1016\/0040-4020(95)00304-Q","article-title":"Sodium Perborate and Sodium Percarbonate: Cheap, Safe\nand Versatile Oxidising Agents for Organic Synthesis","volume":"51","author":"McKillop","year":"1995","journal-title":"Tetrahedron"},{"key":"2026100208364458900_cit35","doi-asserted-by":"publisher","first-page":"189","DOI":"10.1021\/ol990522n","article-title":"The Urea\u2013Hydrogen Peroxide\nComplex: Solid-State\nOxidative Protocols for Hydroxylated Aldehydes and Ketones (Dakin\nReaction), Nitriles, Sulfides, and Nitrogen Heterocycles","volume":"1","author":"Varma","year":"1999","journal-title":"Org. Lett."},{"key":"2026100208364458900_cit36","doi-asserted-by":"publisher","first-page":"1877","DOI":"10.1016\/j.chempr.2020.07.007","article-title":"Late-Stage Functionalization","volume":"6","author":"Bo\u0308rgel","year":"2020","journal-title":"Chem."},{"key":"2026100208364458900_cit37","doi-asserted-by":"publisher","first-page":"522","DOI":"10.1038\/s41570-021-00300-6","article-title":"Late-Stage\nC\u2013H Functionalization Offers New Opportunities in Drug Discovery","volume":"5","author":"Guillemard","year":"2021","journal-title":"Nat. Rev. Chem."},{"key":"2026100208364458900_cit38","doi-asserted-by":"publisher","first-page":"11459","DOI":"10.1021\/acs.jmedchem.4c01347","article-title":"Rational Molecular\nEditing: A New Paradigm in Drug Discovery","volume":"67","author":"Ma","year":"2024","journal-title":"J.\nMed. Chem."},{"key":"2026100208364458900_cit39","doi-asserted-by":"publisher","first-page":"5109","DOI":"10.1002\/cctc.202101345","article-title":"Palladium-Aminopyridine Catalyzed C\u2013H Oxygenation:\nProbing the Nature of Metal Based Oxidant","volume":"13","author":"Lubov","year":"2021","journal-title":"ChemCatChem."},{"key":"2026100208364458900_cit40","doi-asserted-by":"publisher","first-page":"217891","DOI":"10.1016\/j.ccr.2026.217891","article-title":"Selective\nC(sp3)\u2013H Oxyfunctionalizations\nin the Presence of Ru, Rh, and Pd Based Catalysts","volume":"562","author":"Lubov","year":"2026","journal-title":"Coord. Chem. Rev."}],"container-title":["Organic Letters"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.orglett.6c03151","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/orlef7\/article-pdf\/28\/39\/12207\/68562604\/acs.orglett.6c03151.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/orlef7\/article-pdf\/28\/39\/12207\/68562604\/acs.orglett.6c03151.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,2]],"date-time":"2026-10-02T13:03:12Z","timestamp":1790946192000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/orlef7\/article\/28\/39\/12207\/5433187\/Nondirected-Palladium-Catalyzed-C-sp3-H"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,18]]},"references-count":40,"journal-issue":{"issue":"39","published-online":{"date-parts":[[2026,9,18]]},"published-print":{"date-parts":[[2026,10,2]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.orglett.6c03151","relation":{},"ISSN":["1523-7060","1523-7052"],"issn-type":[{"value":"1523-7060","type":"print"},{"value":"1523-7052","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,18]]}}}