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Our strategy first engages azoles using alkenylthianthrenium electrophiles to provide 1,2-azolothianthrenium salts, then selectively excises the sulfonium moiety via single electron transfer (SET). Given that alkenylthianthrenium salts can be readily accessed from alkenes, the net azole addition-hydrogenolysis sequence unlocks a versatile approach to formal Markovnikov alkene hydroazolation. Moreover, the key radical intermediate formed after reduction can be engaged in reactions beyond hydrogen atom transfer (HAT), providing access to carboazolation products that would be otherwise prohibitively difficult to prepare. Mechanistic studies into the reduction of the alkylthianthrenium electrophile implicate an unusual silyl radical attack on DMF that generates a strong SET reductant in situ under otherwise exceedingly mild conditions. Overall, this work introduces new approaches to transform alkylsulfonium building blocks and immediately expands the range of N-alkyl azole molecules that can be readily prepared and studied.<\/jats:p>","DOI":"10.1021\/jacs.6c08262","type":"journal-article","created":{"date-parts":[[2026,7,23]],"date-time":"2026-07-23T17:28:57Z","timestamp":1784827737000},"page":"31641-31648","source":"Crossref","is-referenced-by-count":2,"title":["Formal Markovnikov\nHydroazolation of Alkenes via Reductive\nActivation of Alkylthianthrenium Salts"],"prefix":"10.1021","volume":"148","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4320-4057","authenticated-orcid":true,"given":"Adrian D.","family":"Matthews","sequence":"first","affiliation":[{"name":"University of Wisconsin-Madison , , , ,","place":["Madison, Wisconsin, United States, 53706"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"John R.","family":"Lorenz","sequence":"additional","affiliation":[{"name":"University of Wisconsin-Madison , , , ,","place":["Madison, Wisconsin, United States, 53706"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5733-5288","authenticated-orcid":true,"given":"Zachary K.","family":"Wickens","sequence":"additional","affiliation":[{"name":"University of Wisconsin-Madison , , , ,","place":["Madison, Wisconsin, United States, 53706"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,23]]},"reference":[{"key":"2026080511105563900_cit1a","doi-asserted-by":"publisher","first-page":"730297","DOI":"10.3389\/fcimb.2021.730297","article-title":"Azole Use in Agriculture, Horticulture, and Wood Preservation\n\u2013 Is It Indispensable?","volume":"11","author":"J\u00f8rgensen","year":"2021","journal-title":"Front. 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Med.\nChem."},{"key":"2026080511105563900_cit2","unstructured":"For example, azoles\nspan\nten orders of magnitude in pKa and primary and tertiary\nalkyl groups impose distinct constraints and opportunities."},{"key":"2026080511105563900_cit3","volume-title":"Organic Chemistry","author":"McMurry","year":"2012"},{"issue":"10","key":"2026080511105563900_cit4a","doi-asserted-by":"publisher","first-page":"3451","DOI":"10.1021\/jm200187y","article-title":"The Medicinal Chemist\u2019s Toolbox: An Analysis\nof Reactions Used in the Pursuit of Drug Candidates","volume":"54","author":"Roughley","year":"2011","journal-title":"J. Med. Chem."},{"issue":"10","key":"2026080511105563900_cit4b","doi-asserted-by":"publisher","first-page":"4443","DOI":"10.1021\/acs.jmedchem.5b01409","article-title":"Analysis of Past and Present Synthetic\nMethodologies on Medicinal Chemistry: Where Have All the New Reactions\nGone?: Miniperspective","volume":"59","author":"Brown","year":"2016","journal-title":"J. Med. 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Chem."},{"key":"2026080511105563900_cit13a","doi-asserted-by":"publisher","first-page":"13690","DOI":"10.1039\/D2SC04507A","article-title":"Organothianthrenium Salts: Synthesis and Utilization","volume":"13","author":"Meng","year":"2022","journal-title":"Chem. Sci."},{"key":"2026080511105563900_cit13b","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202314904","article-title":"Alkene Thianthrenation Unlocks Diverse Cation Synthons:\nRecent Progress and New Opportunities","volume":"63","author":"Kim","year":"2024","journal-title":"Angew.\nChem., Int. Ed."},{"key":"2026080511105563900_cit14","unstructured":"We were particularly\ndrawn to polar aprotic solvents since these are the optimal solvents\nfor azole addition into alkenylthianthrenium salts and we ultimately\nintended to develop a one-pot protocol."},{"issue":"21","key":"2026080511105563900_cit15","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202424422","article-title":"Indirect Anti-Markovnikov\nHydrofunctionalization of Terminal Alkenes via an Alkenyl Thianthrenium\nIntermediate","volume":"64","author":"So\u0301va\u0301ri","year":"2025","journal-title":"Angew. Chem., Int. Ed."},{"issue":"1","key":"2026080511105563900_cit16a","doi-asserted-by":"publisher","first-page":"529","DOI":"10.1038\/s41467-024-44746-w","article-title":"Unified Metal-Free Intermolecular Heck-Type Sulfonylation,\nCyanation, Amination, Amidation of Alkenes by Thianthrenation","volume":"15","author":"Liu","year":"2024","journal-title":"Nat. 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Lett."},{"key":"2026080511105563900_cit20","unstructured":"We\nobserved that basic\nadditives such as trialkylamines and formate salts promoted polar\nelimination pathways while Hantzsch-type esters acted as competent\nradical acceptors, scavenging the primary radicals to furnish Minisci-type\nproducts."},{"issue":"40","key":"2026080511105563900_cit21","doi-asserted-by":"publisher","first-page":"8313","DOI":"10.1016\/j.tet.2009.06.091","article-title":"N,N-Dimethylformamide:\nMuch More than a Solvent","volume":"65","author":"Muzart","year":"2009","journal-title":"Tetrahedron"},{"key":"2026080511105563900_cit22","unstructured":"In addition to selective\ndisplacement of the secondary site, generation of the 1,2-azolosulfonium\nsalts from internal alkenes has also been a compounding challenge.\nHowever, we found this readily addressed through the use of a stronger\nBr\u00f8nsted base catalyst (LiOtBu). Using LiOtBu as the base catalyst\nin place of the previously reported Cs2CO3 catalyst\nresults in an approximate 30% boost in yield for the 1,2-azolothianthrenium\nintermediate (see SI for further details)."},{"key":"2026080511105563900_cit23","unstructured":"Reference 12 illustrates\nthat conjugate\naddition to alkenylthianthrenium salts is highly N-regioselective across a wide range of azoles. The study implicates\na Br\u00f8nsted-base catalyzed, reversible conjugate addition as the\norigin of N-regioselectivity."},{"issue":"23","key":"2026080511105563900_cit24","doi-asserted-by":"publisher","first-page":"9309","DOI":"10.1021\/acs.jmedchem.5b01312","article-title":"An Orally\nBioavailable, Indole-3-Glyoxylamide Based Series of Tubulin Polymerization\nInhibitors Showing Tumor Growth Inhibition in a Mouse Xenograft Model\nof Head and Neck Cancer","volume":"58","author":"Colley","year":"2015","journal-title":"J. Med. Chem."},{"key":"2026080511105563900_cit25","unstructured":"For example, the recently\nreported sole example of a hydroazolation method11 found internal alkenes to be challenging substrates with\nrespect to both yield and regioselectivity."},{"key":"2026080511105563900_cit26","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcat.2025.116133","article-title":"Photoelectrochemical Oxidation of Organosilanes to Silanols with\nHigh Selectivity","volume":"447","author":"Qiao","year":"2025","journal-title":"J. Catal."},{"issue":"13","key":"2026080511105563900_cit27","doi-asserted-by":"publisher","first-page":"3066","DOI":"10.1002\/anie.201107334","article-title":"On the Interpretation\nof Deuterium Kinetic Isotope\nEffects in C\u2013H Bond Functionalizations by Transition-Metal\nComplexes","volume":"51","author":"Simmons","year":"2012","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026080511105563900_cit28","unstructured":"Control studies show\nthat AIBN can thermally initiate the process, though with a significantly\nreduced yield. Control experiments excluding either reagent (silane\nor DMF) under these thermal initiation conditions did not provide\nproduct (see SI for full experimental details)."},{"key":"2026080511105563900_cit200","unstructured":"After oxidation of\nthe adduct between the silyl radical and DMF, we suspect that the\nresultant silylium-DMF adduct may be hydrolyzed by adventitious water\nto liberate silanol."},{"issue":"5","key":"2026080511105563900_cit29a","doi-asserted-by":"publisher","first-page":"266","DOI":"10.1021\/acsorginorgau.3c00019","article-title":"High-Throughput Determination of Stern\u2013Volmer\nQuenching Constants for Common Photocatalysts and Quenchers.","volume":"3","author":"Motz","year":"2023","journal-title":"ACS Org. Inorg. Au"},{"issue":"45","key":"2026080511105563900_cit29b","doi-asserted-by":"publisher","first-page":"16161","DOI":"10.1002\/anie.201908718","article-title":"Site-Selective C\u2013H\nOxygenation via Aryl Sulfonium Salts","volume":"58","author":"Sang","year":"2019","journal-title":"Angew.\nChem., Int. Ed."},{"issue":"1","key":"2026080511105563900_cit30","doi-asserted-by":"publisher","first-page":"58","DOI":"10.1002\/anie.201505090","article-title":"Catalysis of Radical\nReactions: A Radical Chemistry\nPerspective","volume":"55","author":"Studer","year":"2016","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026080511105563900_cit31","unstructured":"The\nreaction can be\npromoted without a photocatalyst at 390 nm. At 440 nm wavelengths,\nwe can still observe slow conversion indicating that a photocatalyst\nis not intrinsically required for product formation. See SI for additional details."}],"container-title":["Journal of the American\nChemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacs.6c08262","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/30\/31641\/66238253\/jacs.6c08262.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/30\/31641\/66238253\/jacs.6c08262.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,8,5]],"date-time":"2026-08-05T15:23:36Z","timestamp":1785943416000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jacsat\/article\/148\/30\/31641\/5231281\/Formal-Markovnikov-Hydroazolation-of-Alkenes-via"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,7,23]]},"references-count":68,"journal-issue":{"issue":"30","published-online":{"date-parts":[[2026,7,23]]},"published-print":{"date-parts":[[2026,8,5]]}},"URL":"https:\/\/doi.org\/10.1021\/jacs.6c08262","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,7,23]]}}}