{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,1]],"date-time":"2026-09-01T09:18:35Z","timestamp":1788254315073,"version":"build-2803163510"},"reference-count":90,"publisher":"American Chemical Society (ACS)","issue":"33","license":[{"start":{"date-parts":[[2026,8,13]],"date-time":"2026-08-13T00:00:00Z","timestamp":1786579200000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,8,13]],"date-time":"2026-08-13T00:00:00Z","timestamp":1786579200000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,8,13]],"date-time":"2026-08-13T00:00:00Z","timestamp":1786579200000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100023581","name":"National Science Foundation Graduate Research Fellowship Program","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/100023581","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/na","name":"Acceleration Consortium","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/na","name":"Canada Excellent Research Chairs","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/na","name":"Canadian Foundation for Innovation","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/na","name":"Canadian Institutes of Health Research","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/na","name":"Natural Sciences and Engineering Research Council","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,8,26]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Cyclohexynes are highly strained intermediates that are largely underexplored compared with benzynes, their aromatic counterparts. Known strategies toward generating cyclohexynes include accessing precursors with specific functionalities such as silyl alkenyl triflates, alkenyl halides, alkenyl pseudohalides, diazirines, carbene precursors, or diacyl peroxides, among others. Ultimately, the stepwise buildup of these starting materials and the transient nature of cyclohexynes have led to their synthetic utility being limited to specific classes of reactions, including cycloadditions and nucleophilic trapping. Within this class of strained cycloalkynes, oxacyclohexynes are even more understudied and significantly fewer strategies for their generation exist. Here, we show that 2H-chromynes can be directly accessed from ketones, one of the most abundant and easy-to-install functional groups. The in situ formed 2H-chromynes undergo a subsequent alkyne-ene reaction, an unprecedented mode of reactivity for this strained intermediate. Mechanistic investigations reveal the bifunctional role of phenyl triflimide as both a triflating reagent and a base scavenger. The cyclopentachromene products obtained map onto multiple natural products, including nyingchinoid C, which has yet to be synthesized. To demonstrate the utility of this method, we applied the developed chromyne-ene reaction to a concise total synthesis of nyingchinoid C. The work presented herein highlights an alternative strategy toward generating strained cyclic alkynes and expands their synthetic utility.<\/jats:p>","DOI":"10.1021\/jacs.6c05940","type":"journal-article","created":{"date-parts":[[2026,8,14]],"date-time":"2026-08-14T00:02:02Z","timestamp":1786665722000},"page":"35446-35455","source":"Crossref","is-referenced-by-count":0,"title":["Direct Ketone-to-2\n                    <i>H<\/i>\n                    -Chromyne\nConversion Enabling Alkyne-Ene Reactions and Synthetic Entry into\nthe Nyingchinoid Natural Products"],"prefix":"10.1021","volume":"148","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-5469-9510","authenticated-orcid":true,"given":"Michael R.","family":"Gatazka","sequence":"first","affiliation":[{"name":"University of British Columbia , , 203 Main Mall , , ,","place":["Vancouver, BC, Canada, V6T 1Z1"]},{"name":"University of Michigan , , 930 North University Ave , , ,","place":["Ann Arbor, Michigan, United States, 48109"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Emily F.","family":"Traficante","sequence":"additional","affiliation":[{"name":"University of British Columbia , , 203 Main Mall , , ,","place":["Vancouver, BC, Canada, V6T 1Z1"]},{"name":"University of Michigan , , 930 North University Ave , , ,","place":["Ann Arbor, Michigan, United States, 48109"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8531-0301","authenticated-orcid":true,"given":"Woojin","family":"Lee","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Los Angeles, California, United States, 90095-1569"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Trenton R.","family":"Vogel","sequence":"additional","affiliation":[{"name":"University of British Columbia , , 203 Main Mall , , ,","place":["Vancouver, BC, Canada, V6T 1Z1"]},{"name":"University of Michigan , , 930 North University Ave , , ,","place":["Ann Arbor, Michigan, United States, 48109"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7894-1682","authenticated-orcid":true,"given":"Alistair D.","family":"Richardson","sequence":"additional","affiliation":[{"name":"University of Michigan , , 930 North University Ave , , ,","place":["Ann Arbor, Michigan, United States, 48109"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nicolas","family":"Hernandez","sequence":"additional","affiliation":[{"name":"University of Michigan , , 930 North University Ave , , ,","place":["Ann Arbor, Michigan, United States, 48109"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"K. N.","family":"Houk","sequence":"additional","affiliation":[{"name":"University of California , , , ,","place":["Los Angeles, California, United States, 90095-1569"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4968-8013","authenticated-orcid":true,"given":"Corinna S.","family":"Schindler","sequence":"additional","affiliation":[{"name":"University of British Columbia , , 203 Main Mall , , ,","place":["Vancouver, BC, Canada, V6T 1Z1"]},{"name":"University of British Columbia , , 2350 Health Sciences Mall , , ,","place":["Vancouver, BC, Canada, V6T 1Z3"]},{"name":"BC Cancer Research Institute , 675 West 10th Ave , , ,","place":["Vancouver, BC, Canada, V5Z 1L3"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,13]]},"reference":[{"issue":"13","key":"2026090104500900600_cit1","doi-asserted-by":"publisher","first-page":"3290","DOI":"10.1021\/ja01109a523","article-title":"Rearrangement in the reaction of\nchlorobenzene-1-C14 with potassium amide","volume":"75","author":"Roberts","year":"1953","journal-title":"J. Am. Chem. Soc."},{"issue":"7","key":"2026090104500900600_cit2","doi-asserted-by":"publisher","first-page":"3892","DOI":"10.1021\/acs.chemrev.0c01011","article-title":"o-Silylaryl Triflates:\nA Journey of Kobayashi Aryne Precursors","volume":"121","author":"Shi","year":"2021","journal-title":"Chem.\nRev."},{"issue":"5","key":"2026090104500900600_cit3","doi-asserted-by":"publisher","first-page":"502","DOI":"10.1002\/anie.200390151","article-title":"One Century\nof Aryne Chemistry","volume":"42","author":"Wenk","year":"2003","journal-title":"Angew. Chem., Int. Ed."},{"issue":"16","key":"2026090104500900600_cit4","doi-asserted-by":"publisher","first-page":"3766","DOI":"10.1002\/anie.201107485","article-title":"Arynes and Cyclohexyne\nin Natural Product Synthesis","volume":"51","author":"Gampe","year":"2012","journal-title":"Angew. Chem.,\nInt. Ed."},{"issue":"6","key":"2026090104500900600_cit5","doi-asserted-by":"publisher","first-page":"3550","DOI":"10.1021\/cr200478h","article-title":"A Comprehensive History of Arynes in Natural Product\nTotal Synthesis","volume":"112","author":"Tadross","year":"2012","journal-title":"Chem. Rev."},{"issue":"6","key":"2026090104500900600_cit6","doi-asserted-by":"publisher","first-page":"701","DOI":"10.1016\/S0040-4020(02)01563-6","article-title":"The Use of Arynes in Organic Synthesis","volume":"59","author":"Pellissier","year":"2003","journal-title":"Tetrahedron"},{"issue":"20","key":"2026090104500900600_cit7","doi-asserted-by":"publisher","first-page":"11435","DOI":"10.1021\/acs.chemrev.4c00296","article-title":"Aryne Chemistry:\nGeneration Methods and Reactions Incorporating Multiple Arynes","volume":"124","author":"Kim","year":"2024","journal-title":"Chem. 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Soc."},{"issue":"6694","key":"2026090104500900600_cit9","doi-asserted-by":"publisher","first-page":"408","DOI":"10.1126\/science.adi1606","article-title":"Nickel Binding Enables Isolation and Reactivity of\nPreviously Inaccessible 7-Aza-2,3-Indolynes","volume":"384","author":"Humke","year":"2024","journal-title":"Science"},{"issue":"8095","key":"2026090104500900600_cit10","doi-asserted-by":"publisher","first-page":"91","DOI":"10.1038\/s41586-025-09830-1","article-title":"Myriad Aryne Derivatives\nfrom Carboxylic Acids","volume":"649","author":"Seong","year":"2026","journal-title":"Nature"},{"issue":"51","key":"2026090104500900600_cit11","doi-asserted-by":"publisher","first-page":"46759","DOI":"10.1021\/jacs.5c14686","article-title":"Aryne Generation\nfrom Aryl Halides Via Photothermal Red-Light Activation","volume":"147","author":"Preston-Herrera","year":"2025","journal-title":"J. Am. Chem. 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Soc."},{"issue":"4","key":"2026090104500900600_cit20","doi-asserted-by":"publisher","first-page":"343","DOI":"10.1016\/0040-4020(57)88011-9","article-title":"Evidence for Cyclohexyne\nas an Intermediate in the Coupling of Phenyllithium with 1-Chlorocyclohexene","volume":"1","author":"Scardiglia","year":"1957","journal-title":"Tetrahedron"},{"issue":"3","key":"2026090104500900600_cit21","doi-asserted-by":"publisher","first-page":"704","DOI":"10.1021\/jo01062a014","article-title":"Ring Enlargement Produced by the\nAlkaline Fusion of \u03c9-Bromocamphene","volume":"26","author":"Wolinsky","year":"1961","journal-title":"J.\nOrg. Chem."},{"issue":"5","key":"2026090104500900600_cit22","doi-asserted-by":"publisher","first-page":"1142","DOI":"10.1021\/ja01083a043","article-title":"Rearrangement of Bromomethylenecycloalkanes with Potassium t-Butoxide","volume":"87","author":"Erickson","year":"1965","journal-title":"J. Am. Chem. Soc."},{"issue":"12","key":"2026090104500900600_cit23","doi-asserted-by":"publisher","first-page":"3276","DOI":"10.1002\/cber.19610941214","article-title":"Zur Existenz niedergliedriger\nCycloalkine, II","volume":"94","author":"Wittig","year":"1961","journal-title":"Chem. Ber."},{"issue":"1","key":"2026090104500900600_cit24","doi-asserted-by":"publisher","first-page":"329","DOI":"10.1002\/cber.19630960141","article-title":"Zur Existenz niedergliedriger Cycloalkine, III. Bildung und Verhalten\nvon Cyclohexin","volume":"96","author":"Wittig","year":"1963","journal-title":"Chem. Ber."},{"issue":"1","key":"2026090104500900600_cit25","doi-asserted-by":"publisher","first-page":"342","DOI":"10.1002\/cber.19630960142","article-title":"Zur Existenz niedergliedriger Cycloalkine,\nIV, U\u0308ber die Tetramerisation\ndes Cyclohexins","volume":"96","author":"Wittig","year":"1963","journal-title":"Chem. Ber."},{"issue":"15","key":"2026090104500900600_cit26","doi-asserted-by":"publisher","first-page":"3797","DOI":"10.1021\/ja00744a056","article-title":"Stabilization\nof Small-Ring\nAcetylenes by Complex Formation with Platinum","volume":"93","author":"Bennett","year":"1971","journal-title":"J. Am. Chem. Soc."},{"issue":"6","key":"2026090104500900600_cit27","doi-asserted-by":"publisher","first-page":"1750","DOI":"10.1021\/ja00474a017","article-title":"Synthesis and Reactivity of Zerovalent Platinum Complexes\nof Short-Lived Cyclic Alkynes. Formation of Monomeric Platinum(II)\nHydroxo-, Methoxo-, and \u03c3-Carbon-Bonded Complexes by Oxidative\nAddition Reactions with Water, Methanol, and Activated Hydrocarbons\nand Catalysis of Hydration of Nitriles to Amides","volume":"100","author":"Bennett","year":"1978","journal-title":"J. Am. Chem. Soc."},{"issue":"1","key":"2026090104500900600_cit28","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1016\/S0022-328X(00)81851-3","article-title":"Etude Des Reactions Des Reactifs\nDe Grignard Allyliques Vis a Vis Du Benzyne Et Du Cyclohexyne","volume":"172","author":"Duboudin","year":"1979","journal-title":"J. Organomet. Chem."},{"issue":"12","key":"2026090104500900600_cit29","doi-asserted-by":"publisher","first-page":"4272","DOI":"10.1021\/ja00767a040","article-title":"Rearrangement\nof the Hindered Cyclobutadiene from Dimerization of 3,3,6,6-Tetramethylcyclohexyne","volume":"94","author":"Applequist","year":"1972","journal-title":"J. Am. Chem. Soc."},{"issue":"2","key":"2026090104500900600_cit30","doi-asserted-by":"publisher","first-page":"138","DOI":"10.1002\/anie.196401382","article-title":"Photolysis of 1-Tosylamino-1,2,3-triazole Anions; A\nNew Synthesis of Alkynes","volume":"3","author":"Willey","year":"1964","journal-title":"Angew. Chem., Int.\nEd. Engl."},{"issue":"1","key":"2026090104500900600_cit31","doi-asserted-by":"publisher","first-page":"187","DOI":"10.1016\/0040-4020(72)80068-1","article-title":"Bildung Und Fragmentierung Von Cycloalkeno-1,2,3-selenadiazolen","volume":"28","author":"Meier","year":"1972","journal-title":"Tetrahedron"},{"issue":"12","key":"2026090104500900600_cit32","doi-asserted-by":"publisher","first-page":"3260","DOI":"10.1002\/cber.19610941213","article-title":"Zur Existenz niedergliedriger\nCycloalkine, I","volume":"94","author":"Wittig","year":"1961","journal-title":"Chem. Ber."},{"issue":"6","key":"2026090104500900600_cit33","doi-asserted-by":"publisher","first-page":"1874","DOI":"10.1021\/ja00214a034","article-title":"Benzyne, Cyclohexyne, and 3-Azacyclohexyne and the Problem of Cycloalkyne\nversus Cycloalkylideneketene Genesis","volume":"110","author":"Wentrup","year":"1988","journal-title":"J. Am.\nChem. Soc."},{"issue":"23","key":"2026090104500900600_cit34","doi-asserted-by":"publisher","first-page":"8578","DOI":"10.1021\/ja00179a050","article-title":"1,2,3-Cyclohexatriene\nand Cyclohexen-3-yne: Two New Highly Strained C6H6 Isomers","volume":"112","author":"Shakespeare","year":"1990","journal-title":"J. Am. Chem. Soc."},{"issue":"19","key":"2026090104500900600_cit35","doi-asserted-by":"publisher","first-page":"3039","DOI":"10.1016\/S0040-4039(98)00328-1","article-title":"Generation of Cyclohexyne and its\nDiels-Alder Reaction\nwith \u03b1-Pyrones","volume":"39","author":"Atanes","year":"1998","journal-title":"Tetrahedron Lett."},{"issue":"41","key":"2026090104500900600_cit36","doi-asserted-by":"publisher","first-page":"13214","DOI":"10.1021\/jacs.8b08915","article-title":"Cyclohexenynone Precursors: Preparation\nvia Oxidative Dearomatization Strategy and Reactivity","volume":"140","author":"Qiu","year":"2018","journal-title":"J. Am. Chem. Soc."},{"issue":"6","key":"2026090104500900600_cit37","doi-asserted-by":"publisher","first-page":"3652","DOI":"10.1021\/acs.joc.8b03223","article-title":"Concise Approach to Cyclohexyne and\n1,2-Cyclohexadiene Precursors","volume":"84","author":"Chari","year":"2019","journal-title":"J. Org. Chem."},{"issue":"11","key":"2026090104500900600_cit38","doi-asserted-by":"publisher","first-page":"4500","DOI":"10.1021\/acs.orglett.0c01510","article-title":"Silyl Tosylate\nPrecursors to Cyclohexyne, 1,2-Cyclohexadiene, and 1,2-Cycloheptadiene","volume":"22","author":"McVeigh","year":"2020","journal-title":"Org. Lett."},{"issue":"17","key":"2026090104500900600_cit39","doi-asserted-by":"publisher","first-page":"5474","DOI":"10.1021\/acs.orglett.8b02398","article-title":"Synthesis of Cyclic\n\u03b2-Silylalkenyl\nTriflates via an Alkenyl Cation Intermediate","volume":"20","author":"Lee","year":"2018","journal-title":"Org. Lett."},{"issue":"25","key":"2026090104500900600_cit40","doi-asserted-by":"publisher","first-page":"3343","DOI":"10.1002\/ejoc.201800353","article-title":"One-Pot Synthesis of\nSilylated Enol Triflates from Silyl Enol Ethers for Cyclohexynes and\n1,2-Cyclohexadienes","volume":"2018","author":"Inoue","year":"2018","journal-title":"Eur. J. Org. Chem."},{"issue":"8","key":"2026090104500900600_cit41","doi-asserted-by":"publisher","first-page":"1211","DOI":"10.1246\/cl.1983.1211","article-title":"Fluoride-Induced\n1,2-Elimination of o-Trimethylsilyl-Phenyl Triflate\nto Benzyne Under Mild Conditions","volume":"12","author":"Himeshima","year":"1983","journal-title":"Chem. Lett."},{"issue":"9","key":"2026090104500900600_cit42","doi-asserted-by":"publisher","first-page":"908","DOI":"10.1246\/cl.2002.908","article-title":"Cyclohexynes. Generation from Iodonium\nSalts and Regioselective Reaction with Nucleophile","volume":"31","author":"Fujita","year":"2002","journal-title":"Chem. Lett."},{"issue":"24","key":"2026090104500900600_cit43","doi-asserted-by":"publisher","first-page":"7548","DOI":"10.1021\/ja0496672","article-title":"Elimination\u2013Addition\nMechanism for Nucleophilic Substitution Reaction of Cyclohexenyl Iodonium\nSalts and Regioselectivity of Nucleophilic Addition to the Cyclohexyne\nIntermediate","volume":"126","author":"Fujita","year":"2004","journal-title":"J. Am. Chem. Soc."},{"issue":"8","key":"2026090104500900600_cit44","doi-asserted-by":"publisher","first-page":"679","DOI":"10.1021\/ar040293r","article-title":"Generation of Cycloalkynes\nby Hydro-Iodonio-Elimination of Vinyl Iodonium Salts","volume":"38","author":"Okuyama","year":"2005","journal-title":"Acc. Chem. Res."},{"issue":"17","key":"2026090104500900600_cit45","doi-asserted-by":"publisher","first-page":"2614","DOI":"10.1039\/C6CC09920C","article-title":"Generation\nof Cycloalkynes through Deprotonation of Cyclic Enol Triflates with\nMagnesium Bisamides","volume":"53","author":"Hioki","year":"2017","journal-title":"Chem. Commun."},{"issue":"7","key":"2026090104500900600_cit46","doi-asserted-by":"publisher","first-page":"1298","DOI":"10.1002\/ajoc.201800205","article-title":"Deprotonative Generation\nof Cyclohexynes from Cyclic Enol Triflates Using Aluminate Bases","volume":"7","author":"Hioki","year":"2018","journal-title":"Asian J. Org. Chem."},{"issue":"50","key":"2026090104500900600_cit47","doi-asserted-by":"publisher","first-page":"26332","DOI":"10.1002\/anie.202109482","article-title":"Three-Component Difunctionalization\nof Cyclohexenyl Triflates: Direct Access to Versatile Cyclohexenes\nvia Cyclohexynes","volume":"60","author":"Cho","year":"2021","journal-title":"Angew. 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