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Herein, we constructed the mutant strain \u0394rif-orf3_16::rifR+rif-orf19 by deleting post-PKS modification genes of rifamycin, yielding 34a-deoxyrifamycin W (1a) and its derivatives (2a\u20134a). Subsequent sunlight irradiation of these compounds triggered an intramolecular Paterno\u0300\u2013Bu\u0308chi reaction coupled with Michael addition, producing oxetane-rifamycins A\u2013D (1b\u20134b). They feature a unique 4\/6\/6\/6\/6\/17 hexacyclic scaffold and exhibit potent anti-MRSA activity. Density functional theory (DFT) calculations elucidated the formation mechanism of the oxetane-rifamycin scaffold.<\/jats:p>","DOI":"10.1021\/acs.orglett.6c03401","type":"journal-article","created":{"date-parts":[[2026,8,22]],"date-time":"2026-08-22T00:38:43Z","timestamp":1787359123000},"page":"11148-11154","source":"Crossref","is-referenced-by-count":0,"title":["The Paterno\u0300\u2013Bu\u0308chi\nReaction Diversifies\nRifamycin Scaffolds and Enhances Antibacterial Activity"],"prefix":"10.1021","volume":"28","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1212-6826","authenticated-orcid":true,"given":"Feng","family":"Ye","sequence":"first","affiliation":[{"name":"Shandong Provincial Hospital Affiliated to Shandong First Medical University , , ,","place":["Jinan, China, 250021"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xinyu","family":"Ma","sequence":"additional","affiliation":[{"name":"Shandong University , , , ,","place":["Jinan, Shandong, China, 250012"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhan","family":"Li","sequence":"additional","affiliation":[{"name":"Shandong University , , , ,","place":["Jinan, Shandong, China, 250012"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yanrong","family":"Shi","sequence":"additional","affiliation":[{"name":"Shandong Provincial Hospital Affiliated to Shandong First Medical University , , ,","place":["Jinan, China, 250021"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaochun","family":"Zhang","sequence":"additional","affiliation":[{"name":"Shandong University , , , ,","place":["Jinan, Shandong, China, 250012"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0005-3302-912X","authenticated-orcid":true,"given":"Yanjiao","family":"Ding","sequence":"additional","affiliation":[{"name":"Shandong Second Provincial General Hospital , , , ,","place":["Jinan, Shandong, China, 250022"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3261-1020","authenticated-orcid":true,"given":"Chunhua","family":"Lu","sequence":"additional","affiliation":[{"name":"Shandong University , , , ,","place":["Jinan, Shandong, China, 250012"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8762-9615","authenticated-orcid":true,"given":"Yaoyao","family":"Li","sequence":"additional","affiliation":[{"name":"Shandong University , , , ,","place":["Jinan, Shandong, China, 250012"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7319-4315","authenticated-orcid":true,"given":"Gang","family":"Lu","sequence":"additional","affiliation":[{"name":"Shandong University , , , ,","place":["Jinan, Shandong, China, 250100"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3881-0135","authenticated-orcid":true,"given":"Yuemao","family":"Shen","sequence":"additional","affiliation":[{"name":"Shandong University , , , ,","place":["Jinan, Shandong, China, 250012"]},{"name":"Shandong University , , , ,","place":["Qingdao, Shandong, China, 266237"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,21]]},"reference":[{"key":"2026090409091849700_cit1","doi-asserted-by":"publisher","first-page":"15293","DOI":"10.1021\/jacs.4c02975","article-title":"Enantioselective\nPaterno\u0300\u2013Bu\u0308chi Reactions: Strategic Application\nof a Triplet Rebound Mechanism for Asymmetric Photocatalysis","volume":"146","author":"Kidd","year":"2024","journal-title":"J. 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