{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,12]],"date-time":"2026-10-12T19:48:16Z","timestamp":1791834496269,"version":"4.3.4"},"reference-count":36,"publisher":"American Chemical Society (ACS)","issue":"38","license":[{"start":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T00:00:00Z","timestamp":1789430400000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T00:00:00Z","timestamp":1789430400000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T00:00:00Z","timestamp":1789430400000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22307148"],"award-info":[{"award-number":["22307148"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["82473810"],"award-info":[{"award-number":["82473810"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/na","name":"Fundamental Research Funds for Central Universities, South-Central Minzu University","doi-asserted-by":"publisher","award":["CZQ24022"],"award-info":[{"award-number":["CZQ24022"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/na","name":"Fundamental Research Funds for Central Universities, South-Central Minzu University","doi-asserted-by":"publisher","award":["GLCZH25039"],"award-info":[{"award-number":["GLCZH25039"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,9,25]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Chamigranes are a unique class of sesquiterpenoids featuring a spiro[5.5]undecane framework, yet their biosynthesis in fungi has remained elusive for decades. In this study, we identify and characterize ChamTS, a sesquiterpene synthase from the basidiomycetous fungus Cerrena albocinnamomea, which specifically catalyzes the formation of (+)-\u03b2-chamigrane. In vitro isotope-labeling experiments unveiled the cyclization pathway of ChamTS, revealing an initial 1,6-cyclization followed by a 1,5-proton shift and spirocycle-forming rearrangement. This work provides a foundation for the biosynthetic production and further engineering of \u03b2-chamigrane-type terpenoids.<\/jats:p>","DOI":"10.1021\/acs.orglett.6c03630","type":"journal-article","created":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T20:02:02Z","timestamp":1789502522000},"page":"12106-12112","source":"Crossref","is-referenced-by-count":0,"title":["Identification\nand Cyclization Mechanism of Fungal\n(+)-\u03b2-Chamigrene Synthase"],"prefix":"10.1021","volume":"28","author":[{"given":"Yang","family":"Gao","sequence":"first","affiliation":[{"name":"South-Central Minzu University , , ,","place":["Wuhan, China, 430074"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Li-Li","family":"Guo","sequence":"additional","affiliation":[{"name":"South-Central Minzu University , , ,","place":["Wuhan, China, 430074"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Subiy","family":"Akbar","sequence":"additional","affiliation":[{"name":"South-Central Minzu University , , ,","place":["Wuhan, China, 430074"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhiyuan","family":"Zhou","sequence":"additional","affiliation":[{"name":"South-Central Minzu University , , ,","place":["Wuhan, China, 430074"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Weiping","family":"Zhang","sequence":"additional","affiliation":[{"name":"South-Central Minzu University , , ,","place":["Wuhan, China, 430074"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xinyang","family":"Li","sequence":"additional","affiliation":[{"name":"South-Central Minzu University , , ,","place":["Wuhan, China, 430074"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0416-9535","authenticated-orcid":true,"given":"He-Ping","family":"Chen","sequence":"additional","affiliation":[{"name":"South-Central Minzu University , , ,","place":["Wuhan, China, 430074"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ji-Kai","family":"Liu","sequence":"additional","affiliation":[{"name":"South-Central Minzu University , , ,","place":["Wuhan, China, 430074"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,15]]},"reference":[{"key":"2026101215063407200_cit1","doi-asserted-by":"publisher","first-page":"28","DOI":"10.1039\/D2NP00020B","article-title":"Engineering Fungal Terpene Biosynthesis","volume":"40","author":"Yin","year":"2023","journal-title":"Nat. Prod. Rep."},{"key":"2026101215063407200_cit2","doi-asserted-by":"publisher","first-page":"766","DOI":"10.1039\/D2NP00076H","article-title":"Terpene\nSynthases and Pathways in Animals: Enzymology and Structural Evolution\nin the Biosynthesis of Volatile Infochemicals","volume":"40","author":"Tholl","year":"2023","journal-title":"Nat. Prod. Rep."},{"key":"2026101215063407200_cit3","doi-asserted-by":"publisher","first-page":"12774","DOI":"10.1021\/acscatal.3c03047","article-title":"Decoding\nCatalysis by Terpene Synthases","volume":"13","author":"Whitehead","year":"2023","journal-title":"ACS Catal."},{"key":"2026101215063407200_cit4","doi-asserted-by":"publisher","first-page":"6670","DOI":"10.1021\/acs.orglett.4c02351","article-title":"Biosynthesis of\nthe Sesquiterpenoid Malfilanol D in Aspergillus ustus Implies Alkyl and Hydride Migrations during the Bicyclo[5.4.0]undecane\nSkeleton Formation","volume":"26","author":"Peter","year":"2024","journal-title":"Org. Lett."},{"key":"2026101215063407200_cit5","doi-asserted-by":"publisher","first-page":"4475","DOI":"10.1021\/acs.orglett.4c01272","article-title":"Emerindanols\nA and B: Two Bipolyhydroindenol\nSesterterpenes with 5\/6\u20136\/5 Coupled Ring System Discovered\nby Genome Mining","volume":"26","author":"Liu","year":"2024","journal-title":"Org. Lett."},{"key":"2026101215063407200_cit6","doi-asserted-by":"publisher","first-page":"338","DOI":"10.1021\/acs.orglett.3c04005","article-title":"Genome Mining Reveals\nthe Biosynthesis of Sativene and Its Oxidative Conversion to seco-Sativene","volume":"26","author":"Zhang","year":"2024","journal-title":"Org. Lett."},{"key":"2026101215063407200_cit7","doi-asserted-by":"publisher","first-page":"1686","DOI":"10.1021\/acs.orglett.5c00062","article-title":"Genome Mining\nand Biosynthesis of Fungal Africane-Type Sesquiterpenes","volume":"27","author":"Xu","year":"2025","journal-title":"Org. Lett."},{"key":"2026101215063407200_cit8","doi-asserted-by":"publisher","first-page":"13110","DOI":"10.1021\/acs.orglett.5c04272","article-title":"Biosynthesis of Trichobisabolins\nInvolves a UbiA-Type\nTerpene Cyclase for trans-Zingiberenol Generation and a Single Cytochrome\nP450 Catalyzing the \u03b3-Butenolide Formation from an Isoprene\nUnit","volume":"27","author":"Shen","year":"2025","journal-title":"Org. Lett."},{"key":"2026101215063407200_cit9","doi-asserted-by":"publisher","first-page":"6211","DOI":"10.1021\/acs.orglett.5c01879","article-title":"Expanding\nthe Diversity of the Terpene Skeleton and Structure through Identification\nof Noncanonical Class IE and IF Terpene Synthase-Formed Products","volume":"27","author":"Abe","year":"2025","journal-title":"Org. Lett."},{"key":"2026101215063407200_cit10","doi-asserted-by":"publisher","first-page":"3747","DOI":"10.1021\/acs.orglett.5c00926","article-title":"Unveiling\nthe Biosynthesis of Sphaerols A\u2013E: Catalyzed by Two Uncommon\nDiterpene Synthases AsSS and CvSS","volume":"27","author":"Lu","year":"2025","journal-title":"Org. Lett."},{"key":"2026101215063407200_cit11","doi-asserted-by":"publisher","first-page":"6703","DOI":"10.1021\/jacs.2c01971","article-title":"Catalytic Asymmetric\nSpirocyclizing Diels\u2013Alder Reactions of Enones: Stereoselective\nTotal and Formal Syntheses of \u03b1-Chamigrene, \u03b2-Chamigrene,\nLaurencenone C, Colletoic Acid, and Omphalic Acid","volume":"144","author":"Ghosh","year":"2022","journal-title":"J. Am. Chem. Soc."},{"key":"2026101215063407200_cit12","doi-asserted-by":"publisher","first-page":"186b","DOI":"10.1039\/C1967000186B","article-title":"Chamigrene,\na Sesquiterpene Hydrocarbon of a Novel Carbon Skeleton","volume":"3","author":"Ito","year":"1967","journal-title":"Chem. Commun. (London)"},{"key":"2026101215063407200_cit13","doi-asserted-by":"publisher","first-page":"2483","DOI":"10.1016\/S0040-4039(00)76162-4","article-title":"New Sesquiterpenoids from Schisandra chinensis","volume":"9","author":"Ohta","year":"1968","journal-title":"Tetrahedron Lett."},{"key":"2026101215063407200_cit14","doi-asserted-by":"publisher","first-page":"3632","DOI":"10.1021\/cr9002215","article-title":"Halogenated Organic\nMolecules of Rhodomelaceae Origin: Chemistry and Biology","volume":"113","author":"Wang","year":"2013","journal-title":"Chem. Rev."},{"key":"2026101215063407200_cit15","doi-asserted-by":"publisher","first-page":"3152","DOI":"10.1016\/j.tetlet.2010.04.048","article-title":"Two Novel Norsesquiterpene\nPeroxides from Basidiomycete Steccherinum ochraceum","volume":"51","author":"Liu","year":"2010","journal-title":"Tetrahedron Lett."},{"key":"2026101215063407200_cit16","doi-asserted-by":"publisher","first-page":"1005","DOI":"10.1021\/np100103j","article-title":"Cytotoxic Nor-Chamigrane\nand Chamigrane Endoperoxides\nfrom a Basidiomycetous Fungus","volume":"73","author":"Chokpaiboon","year":"2010","journal-title":"J. Nat. Prod."},{"key":"2026101215063407200_cit17","doi-asserted-by":"publisher","first-page":"114904","DOI":"10.1016\/j.phytochem.2026.114904","article-title":"Antihyperglycemic Nor-Chamigrane\nSesquiterpenoids from the Fungus Antrodiella albocinnamomea","volume":"248","author":"Liu","year":"2026","journal-title":"Phytochemistry"},{"key":"2026101215063407200_cit18","doi-asserted-by":"publisher","first-page":"113830","DOI":"10.1016\/j.phytochem.2023.113830","article-title":"Steccherins A\u2013D,\nChamigrane-Type Sesquiterpenes\nfrom the Fungus Steccherinum ochraceum with Selective\nInhibition on B Lymphocyte Proliferation","volume":"214","author":"Huang","year":"2023","journal-title":"Phytochemistry"},{"key":"2026101215063407200_cit19","doi-asserted-by":"publisher","DOI":"10.1371\/journal.pone.0046172","article-title":"Hit-to-Lead\nDevelopment of the Chamigrane Endoperoxide Merulin A for the Treatment\nof African Sleeping Sickness","volume":"7","author":"Navarro","year":"2012","journal-title":"PLoS One"},{"key":"2026101215063407200_cit20","doi-asserted-by":"publisher","first-page":"10415","DOI":"10.1074\/jbc.RA118.007231","article-title":"The Natural\nProduct Antroalbol H\nPromotes Phosphorylation of Liver Kinase B1 (LKB1) at Threonine 189\nand Thereby Enhances Cellular Glucose Uptake","volume":"294","author":"Wang","year":"2019","journal-title":"J. Biol. Chem."},{"key":"2026101215063407200_cit21","doi-asserted-by":"publisher","first-page":"103944","DOI":"10.1016\/j.fgb.2024.103944","article-title":"Efficient Genome\nEditing Using CRISPR\/Cas9\nTechnology and Its Application for Identifying Sesquiterpene Synthases\nInvolved in the Biosynthesis of Steperoxides in Steccherinum ochraceum","volume":"175","author":"Shen","year":"2024","journal-title":"Fungal Genet. Biol."},{"key":"2026101215063407200_cit22","doi-asserted-by":"publisher","first-page":"110031","DOI":"10.1016\/j.plaphy.2025.110031","article-title":"Characterization\nof Microbial-Type\nTerpene Synthases from Two Liverworts Lophocolea bidentata and Nardia scalaris","volume":"226","author":"Conart","year":"2025","journal-title":"Plant\nPhysiol. Biochem."},{"key":"2026101215063407200_cit23","doi-asserted-by":"publisher","first-page":"185","DOI":"10.1021\/acschembio.3c00627","article-title":"Biosynthesis\nof Haloterpenoids in Red Algae via Microbial-like Type I Terpene Synthases","volume":"19","author":"Steele","year":"2024","journal-title":"ACS Chem. Biol."},{"key":"2026101215063407200_cit24","doi-asserted-by":"publisher","first-page":"2480","DOI":"10.1002\/cbic.201300349","article-title":"Mushroom Hunting by Using Bioinformatics: Application\nof a Predictive Framework Facilitates the Selective Identification\nof Sesquiterpene Synthases in Basidiomycota","volume":"14","author":"Quin","year":"2013","journal-title":"ChemBioChem."},{"key":"2026101215063407200_cit25","doi-asserted-by":"publisher","first-page":"772","DOI":"10.1016\/j.chembiol.2012.05.012","article-title":"Draft Genome of Omphalotus olearius Provides a Predictive Framework for Sesquiterpenoid Natural Product\nBiosynthesis in Basidiomycota","volume":"19","author":"Wawrzyn","year":"2012","journal-title":"Chem. Biol."},{"key":"2026101215063407200_cit26","doi-asserted-by":"publisher","first-page":"W435","DOI":"10.1093\/nar\/gkl200","article-title":"AUGUSTUS: Ab Initio Prediction of\nAlternative Transcripts","volume":"34","author":"Stanke","year":"2006","journal-title":"Nucleic Acids Res."},{"key":"2026101215063407200_cit27","doi-asserted-by":"publisher","first-page":"1396","DOI":"10.1002\/bit.25198","article-title":"In Vitro Reconstitution\nof Mevalonate Pathway and\nTargeted Engineering of Farnesene Overproduction in Escherichia coli","volume":"111","author":"Zhu","year":"2014","journal-title":"Biotechnol. Bioeng."},{"key":"2026101215063407200_cit28","doi-asserted-by":"publisher","first-page":"27","DOI":"10.1007\/s13659-025-00578-9","article-title":"Genome Mining and\nFunctional Characterization of Four Type I Sesquiterpene Synthases\nfrom the Tiger Milk Mushroom Lignosus rhinocerus","volume":"16","author":"Gao","year":"2026","journal-title":"Nat. Prod. Bioprospect."},{"key":"2026101215063407200_cit29","doi-asserted-by":"publisher","first-page":"36942","DOI":"10.1021\/jacs.6c10016","article-title":"Biosynthesis\nof Crinipellin Diterpenes in Mushroom Marasmius fiardii PR-910","volume":"148","author":"Guo","year":"2026","journal-title":"J. Am. Chem.\nSoc."},{"key":"2026101215063407200_cit30","doi-asserted-by":"publisher","first-page":"2493","DOI":"10.1021\/acs.joc.4c03119","article-title":"Cyclic Osmate Esters from 1,2- and\n1,3-Diols and \u03b1-Hydroxy Acids for X-ray Analysis","volume":"90","author":"Thompson","year":"2025","journal-title":"J. Org. Chem."},{"key":"2026101215063407200_cit31","doi-asserted-by":"publisher","first-page":"163","DOI":"10.1016\/bs.mie.2024.01.011","article-title":"Isotopic Labelings for Mechanistic Studies","volume":"699","author":"Xu","year":"2024","journal-title":"Methods Enzymol."},{"key":"2026101215063407200_cit32","doi-asserted-by":"publisher","first-page":"10821","DOI":"10.1021\/acs.orglett.5c03451","article-title":"Mechanistic\nCharacterization of a\nTerpene Synthase for a Diterpene Diol from Chitinophaga jiangningensis","volume":"27","author":"Tabekoueng","year":"2025","journal-title":"Org. Lett."},{"key":"2026101215063407200_cit33","doi-asserted-by":"publisher","first-page":"2776","DOI":"10.1002\/anie.201612439","article-title":"Mechanistic\nInvestigations of Two\nBacterial Diterpene Cyclases: Spiroviolene Synthase and Tsukubadiene\nSynthase","volume":"56","author":"Rabe","year":"2017","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026101215063407200_cit34","doi-asserted-by":"publisher","first-page":"15887","DOI":"10.1002\/anie.201809954","article-title":"A Clade\nII-D Fungal Chimeric Diterpene Synthase from Colletotrichum gloeosporioides Produces Dolasta-1(15),8-diene","volume":"57","author":"Bian","year":"2018","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026101215063407200_cit35","doi-asserted-by":"publisher","first-page":"10501","DOI":"10.1002\/chem.201702704","article-title":"Mechanistic Studies of Terpene Cyclases","volume":"23","author":"Rinkel","year":"2017","journal-title":"Chem.-Eur. J."},{"key":"2026101215063407200_cit36","doi-asserted-by":"publisher","first-page":"2450","DOI":"10.1021\/ja4106489","article-title":"Branching Out from the Bisabolyl Cation. Unifying Mechanistic\nPathways to Barbatene, Bazzanene, Chamigrene, Chamipinene, Cumacrene,\nCuprenene, Dunniene, Isobazzanene, Iso-\u03b3-bisabolene, Isochamigrene,\nLaurene, Microbiotene, Sesquithujene, Sesquisabinene, Thujopsene,\nTrichodiene, and Widdradiene Sesquiterpenes","volume":"136","author":"Hong","year":"2014","journal-title":"J. Am. Chem. Soc."}],"container-title":["Organic Letters"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.orglett.6c03630","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/orlef7\/article-pdf\/28\/38\/12106\/68521603\/acs.orglett.6c03630.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/orlef7\/article-pdf\/28\/38\/12106\/68521603\/acs.orglett.6c03630.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,12]],"date-time":"2026-10-12T19:12:46Z","timestamp":1791832366000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/orlef7\/article\/28\/38\/12106\/5430625\/Identification-and-Cyclization-Mechanism-of-Fungal"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,15]]},"references-count":36,"journal-issue":{"issue":"38","published-online":{"date-parts":[[2026,9,15]]},"published-print":{"date-parts":[[2026,9,25]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.orglett.6c03630","relation":{},"ISSN":["1523-7060","1523-7052"],"issn-type":[{"value":"1523-7060","type":"print"},{"value":"1523-7052","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,15]]}}}