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While its biosynthesis is catalyzed by 7\u2010\n                    <jats:italic>epi<\/jats:italic>\n                    \u2010zingiberene synthase from the noncanonical terpene precursor (2\n                    <jats:italic>Z<\/jats:italic>\n                    ,6\n                    <jats:italic>Z<\/jats:italic>\n                    )\u2010farnesyl pyrophosphate (\n                    <jats:bold>5a<\/jats:bold>\n                    ), the precise enzymatic mechanism has remained undetermined. Using deuterated substrates generated chemoenzymatically, the 1,6\u2010cyclization mechanism was established to proceed via a 1,3\u2010hydride shift from the C1 position of the initial bisabolyl carbocationic intermediate. Product diversity was expanded by identifying two single residue switches within the G1\/2 helix that govern enzyme fidelity, thereby redirecting product distributions to alternative C6\u2010cyclized zingiberenols as well as \u03b3\u2010 and \u03b2\u2010curcumene. Applying this chemoenzymatic synthesis with alternative allyl alcohols plus isoprenol enabled the production and structural diversification of two novel\n                    <jats:italic>nor<\/jats:italic>\n                    \u2010sesquiterpene analogs (C\n                    <jats:sub>14<\/jats:sub>\n                    \/C\n                    <jats:sub>16<\/jats:sub>\n                    ), 13\u2010\n                    <jats:italic>nor<\/jats:italic>\n                    \u2010(4\n                    <jats:italic>R<\/jats:italic>\n                    ,7\n                    <jats:italic>R<\/jats:italic>\n                    )\u2010zingiberene (\n                    <jats:bold>23<\/jats:bold>\n                    ) and 12\u2010ethyl\u201013\u2010\n                    <jats:italic>nor<\/jats:italic>\n                    \u2010(4\n                    <jats:italic>R<\/jats:italic>\n                    ,7\n                    <jats:italic>R<\/jats:italic>\n                    )\u2010zingiberene (\n                    <jats:bold>24<\/jats:bold>\n                    ). Notably, these syntheses were only possible because the tomato (2\n                    <jats:italic>Z<\/jats:italic>\n                    ,6\n                    <jats:italic>Z<\/jats:italic>\n                    )\u2010farnesyl pyrophosphate synthase overcomes conventional prenyltransferase substrate selectivity to catalyze chain extension via atypical secondary allyl carbocation intermediates. The catalytic promiscuity provides opportunities to engineer terpene products with diverse methyl\u2010branching patterns, providing the platform to investigate the molecular basis of terpene semiochemical activity needed for the development of broad\u2010spectrum repellents to sustainably manage insect pests in agriculture.\n                  <\/jats:p>","DOI":"10.1002\/cbic.70534","type":"journal-article","created":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T18:06:04Z","timestamp":1791309964000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Chemoenzymatic Synthesis of (4\n                    <i>R<\/i>\n                    ,7\n                    <i>R<\/i>\n                    )\u2010Zingiberene Enables Construction of\n                    <i>nor<\/i>\n                    \u2010Sesquiterpene Semiochemical Analogs"],"prefix":"10.1002","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6697-6589","authenticated-orcid":false,"given":"Luke A.","family":"Johnson","sequence":"first","affiliation":[{"name":"School of Chemistry Cardiff University  Cardiff UK"},{"name":"School of Biomolecular and Biomedical Sciences University College Dublin  Belfield, Dublin 4 Ireland"},{"name":"UCD Conway Institute, University College Dublin  Belfield, Dublin 4 Ireland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jennifer C. R.","family":"Benton","sequence":"additional","affiliation":[{"name":"School of Chemistry Cardiff University  Cardiff UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chris","family":"Jones","sequence":"additional","affiliation":[{"name":"School of Chemistry Cardiff University  Cardiff UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0009-8902-3332","authenticated-orcid":false,"given":"Oktawia","family":"Kuzba","sequence":"additional","affiliation":[{"name":"School of Chemistry Cardiff University  Cardiff UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4956-2656","authenticated-orcid":false,"given":"David J.","family":"Miller","sequence":"additional","affiliation":[{"name":"School of Chemistry Cardiff University  Cardiff UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8386-3770","authenticated-orcid":false,"given":"John 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