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Although some linear chain \u03b2,\u03b3\u2010alkanediols beside butane\u20102,3\u2010diol are naturally present, their biosynthetic pathways remain underexplored. In this study, we expand the acetohydroxyacid synthase (AHAS)\u2010mediated carboligation for the synthesis of linear chain \u03b2,\u03b3\u2010alkanediols in\n                    <jats:italic>Escherichia coli<\/jats:italic>\n                    , namely, hexane\u20102,3\u2010diol (2,3\u2010HDO) and pentane\u20102,3\u2010diol (2,3\u2010PDO). Two pathways for the production of 2,3\u2010HDO (a redesigned\n                    <jats:italic>Clostridium<\/jats:italic>\n                    \u2010derived clostridial pathway and an artificial reversal \u03b2\u2010oxidation pathway) were developed, and the engineered\n                    <jats:italic>E. coli<\/jats:italic>\n                    cells with further disruption of endogenous thioesterases produced 152.2\u00a0m\n                    <jats:sc>m<\/jats:sc>\n                    (17.98\u00a0g\/L) 2,3\u2010HDO from 60.03\u00a0g\/L glucose in the fed\u2010batch bioreactor. We also expand the similar design for 2,3\u2010PDO biosynthesis, achieving 15.5\u00a0m\n                    <jats:sc>m<\/jats:sc>\n                    (1.61\u00a0g\/L) in shake flasks. This work demonstrates the great versatility of the AHAS\u2010mediated carboligation for the synthesis of linear chain \u03b2,\u03b3\u2010alkanediols, which would pave its way for the future production of other linear chain \u03b2,\u03b3\u2010diols from renewable feedstocks.\n                  <\/jats:p>","DOI":"10.1002\/advs.202519742","type":"journal-article","created":{"date-parts":[[2026,2,12]],"date-time":"2026-02-12T14:18:26Z","timestamp":1770905906000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Engineering New\u2010to\u2010Nature Biological Pathways for \u03b2,\u03b3\u2010Alkanediol Synthesis"],"prefix":"10.1002","volume":"13","author":[{"given":"Haofeng","family":"Chen","sequence":"first","affiliation":[{"name":"State Key Laboratory of Cellular Stress Biology School of Life Sciences Faculty of Medicine and Life Sciences Xiamen University  Fujian 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