{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,26]],"date-time":"2026-08-26T07:44:04Z","timestamp":1787730244371,"version":"build-2784847793"},"reference-count":25,"publisher":"Wiley","issue":"10","license":[{"start":{"date-parts":[[2026,4,7]],"date-time":"2026-04-07T00:00:00Z","timestamp":1775520000000},"content-version":"am","delay-in-days":365,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#am"},{"start":{"date-parts":[[2025,4,7]],"date-time":"2025-04-07T00:00:00Z","timestamp":1743984000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["CHE\u20102152633"],"award-info":[{"award-number":["CHE\u20102152633"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["J Comput Chem"],"published-print":{"date-parts":[[2025,4,15]]},"abstract":"<jats:title>ABSTRACT<\/jats:title><jats:p>Access to benzofuran\u20102(3H)\u2010one derivatives from readily available substrates under mild conditions is crucial in the pharmaceutical and plastics industries. We identified (Z)\u20103\u2010(2\u2010phenylhydrazineylidene)benzofuran\u20102(3H)\u2010one (<jats:bold>P<\/jats:bold>) during the recrystallization of (E)\u20102\u2010(2,2\u2010dichloro\u20101\u2010(phenyldiazenyl)vinyl)phenol using a 96% ethanol solution. The mechanism of the unexpected substrate conversion leading to <jats:bold>P<\/jats:bold> is investigated using density functional calculations. The computations revealed that ethanol is required to initiate the reaction via <jats:bold>TS1E<\/jats:bold>, which involves a concerted deprotonation of ethanol by the basic diaza group of the substrate and an ethoxy group attacking the electrophilic center (Cl<jats:sub>2<\/jats:sub>C\uf8fe), with an energy barrier of 28.3\u2009kcal\/mol. The resulting intermediate (<jats:bold>I1E<\/jats:bold>) is calculated to be unstable and can yield a cyclic chloroacetal adduct with a lower energy barrier of 2.2\u2009kcal\/mol via the ring\u2010closure transition state (<jats:bold>TS2E<\/jats:bold>). In the absence of water, the next steps are impossible because water is required to cleave the ether bond, yielding <jats:bold>P<\/jats:bold>. A small amount of water (4% of the recrystallization solvent) can promote further transformation of <jats:bold>I2E<\/jats:bold> via the transition states <jats:bold>TS3E<\/jats:bold> (\u2206<jats:italic>G<\/jats:italic><jats:sup>\u2021<\/jats:sup>\u2009=\u200911.1\u2009kcal\/mol) and <jats:bold>TS4E<\/jats:bold> (\u2206<jats:italic>G<\/jats:italic><jats:sup>\u2021<\/jats:sup>\u2009=\u200910.5\u2009kcal\/mol). A comparison of the ethanol\/water\u2010 and only water\u2010promoted free energy profiles shows that the presence of ethanol is crucial for lowering the energy barriers (by about 5\u2009kcal\/mol) for the initial two steps leading to the cyclic chloroacetal (<jats:bold>I2E<\/jats:bold>), whereas water is then required to initiate product formation.<\/jats:p>","DOI":"10.1002\/jcc.70102","type":"journal-article","created":{"date-parts":[[2025,4,7]],"date-time":"2025-04-07T11:09:05Z","timestamp":1744024145000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Can Water Trigger Room\u2010Temperature Formation of Benzofuran\u20102(<scp>3H<\/scp>)\u2010one Scaffolds From Vinyldiazene Derivatives? Computational Insights Into an Unusual Cyclization"],"prefix":"10.1002","volume":"46","author":[{"given":"Ulviyya","family":"Askerova","sequence":"first","affiliation":[{"name":"Organic Chemistry Department Baku State University  Baku Azerbaijan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yusif","family":"Abdullayev","sequence":"additional","affiliation":[{"name":"Division of Mathematics and Natural Sciences Allen University  Columbia South Carolina USA"},{"name":"Department of Chemical Engineering Baku Engineering University  Baku Absheron Azerbaijan"},{"name":"Institute of Petrochemical Processes, Azerbaijan National Academy of Sciences  Baku Azerbaijan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Namiq","family":"Shikhaliyev","sequence":"additional","affiliation":[{"name":"Department of Chemical Engineering Baku Engineering University  Baku Absheron Azerbaijan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Avtandil","family":"Talybov","sequence":"additional","affiliation":[{"name":"Institute of Petrochemical Processes, Azerbaijan National Academy of Sciences  Baku Azerbaijan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jochen","family":"Autschbach","sequence":"additional","affiliation":[{"name":"Department of Chemistry University at Buffalo, State University of New York  Buffalo New York USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,4,7]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/jm9002439"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.foodchem.2023.137487"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/bio.4854"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/cjoc.202400244"},{"key":"e_1_2_8_6_1","first-page":"1","article-title":"Recent Progress on Natural \u03b1\u2010Glucosidase Inhibitors Derived From the Plants and Microorganisms","volume":"31","author":"Deng C.","year":"2024","journal-title":"Current Medicinal Chemistry"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/s0141\u20103910(02)00141\u20106"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.202200396"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201902985"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1002\/cjoc.201200809"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.5b02177"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.8b02555"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.2c00325"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.3390\/molecules25215013"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.27433"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1134\/s1070428020020013"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1107\/s2056989021011749"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1107\/s2056989021007891"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202402886"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.molstruc.2024.139460"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.8b02402"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/slct.201803390"},{"key":"e_1_2_8_23_1","volume-title":"Gaussian 16, Revision C.01","author":"Frisch M. 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