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Herein, we report a visible light-driven strategy that repurposes water as an extrinsic oxygen source to enable divergent access to two classes of tetrasubstituted 4H-pyrans from readily available 5-alkynyl ketones and sulfonyl chlorides. Using inexpensive 4CzIPN, this protocol delivers over 40 examples in up to 72% yield. Mechanistic studies (X-ray corroborated) reveal photoinduced water-mediated oxysulfonylation of unactivated alkynes as the pivotal branching step. Synthetic utility is demonstrated through late-stage functionalization, gram-scale operation, and facile conversion to structurally diverse 6- and 7-membered heterocycles.<\/jats:p>","DOI":"10.1021\/acs.orglett.6c03508","type":"journal-article","created":{"date-parts":[[2026,9,12]],"date-time":"2026-09-12T16:01:42Z","timestamp":1789228902000},"page":"12005-12010","source":"Crossref","is-referenced-by-count":0,"title":["Tapping Water\nas an Oxygen Source: Visible-Light-Driven\nSynthesis of 4\n                    <i>H<\/i>\n                    -Pyrans from 5-Alkynyl\nKetones and Sulfonyl Chlorides"],"prefix":"10.1021","volume":"28","author":[{"given":"Yu-Jie","family":"Cao","sequence":"first","affiliation":[{"name":"Jiangsu Ocean University , , Cangwu Road 59 , , ,","place":["Lianyungang, Jiangsu, China, 222005"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Li-Bo","family":"Wu","sequence":"additional","affiliation":[{"name":"Jiangsu Ocean University , , Cangwu Road 59 , , ,","place":["Lianyungang, Jiangsu, China, 222005"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jun-Hang","family":"Li","sequence":"additional","affiliation":[{"name":"Jiangsu Ocean University , , Cangwu Road 59 , , ,","place":["Lianyungang, Jiangsu, China, 222005"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Min","family":"Gu","sequence":"additional","affiliation":[{"name":"Jiangsu Ocean University , , Cangwu Road 59 , , ,","place":["Lianyungang, Jiangsu, China, 222005"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4565-4230","authenticated-orcid":true,"given":"Quan-Qing","family":"Zhao","sequence":"additional","affiliation":[{"name":"Jiangsu Ocean University , , Cangwu Road 59 , , ,","place":["Lianyungang, Jiangsu, China, 222005"]},{"name":"Sinopep-Allsino Biopharmaceutical Co., Ltd. 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Organomet. Chem."},{"key":"2026092510101730900_cit15b","doi-asserted-by":"publisher","first-page":"14558","DOI":"10.1039\/D4RA07788A","article-title":"Recent advances in the application of \u03b2-ketonitriles as multifunctional intermediates in organic chemistry","volume":"15","author":"Rostampoor","year":"2025","journal-title":"RSC Adv."},{"key":"2026092510101730900_cit15c","doi-asserted-by":"publisher","DOI":"10.1002\/slct.202501023","article-title":"Synthetic Strategies\nToward 2H-, 4H-Pyrans, and Pyranones:\nRecent Advances","volume":"10","author":"Samai","year":"2025","journal-title":"ChemistrySelect"},{"key":"2026092510101730900_cit16a","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202420671","article-title":"Visible-Light Photocatalyzed Skeletal Rearrangement Enables the Synthesis\nof Highly Functionalized Xanthenes with Antitumor Activity","volume":"64","author":"Lin","year":"2025","journal-title":"Angew. Chem., Int. 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Lett."},{"key":"2026092510101730900_cit24","doi-asserted-by":"publisher","first-page":"2772","DOI":"10.1039\/D1GC04686A","article-title":"Thermoneutral synthesis of spiro-1,4-cyclohexadienes\nby visible-light-driven dearomatization of benzylmalonates","volume":"24","author":"Zhao","year":"2022","journal-title":"Green Chem."},{"key":"2026092510101730900_cit25","doi-asserted-by":"publisher","first-page":"14398","DOI":"10.1021\/acscatal.2c04736","article-title":"Divergent and Synergistic\nPhotocatalysis: Hydro- and Oxoalkylation of Vinyl Arenes for the Stereoselective\nSynthesis of Cyclopentanols via a Formal [4 + 1]-Annulation of 1,3-Dicarbonyls","volume":"12","author":"Katta","year":"2022","journal-title":"ACS Catal."},{"key":"2026092510101730900_cit26","doi-asserted-by":"publisher","first-page":"171","DOI":"10.1002\/cjoc.70285","article-title":"Visible-Light-Driven\n1,4-Hydroalkylation of 1,3-Conjugated Dienes with 1,3-Dicarbonyls","volume":"44","author":"Gu","year":"2026","journal-title":"Chin. 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