{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,23]],"date-time":"2026-10-23T19:45:28Z","timestamp":1792784728886,"version":"4.5.0"},"reference-count":68,"publisher":"American Chemical Society (ACS)","issue":"40","license":[{"start":{"date-parts":[[2026,9,26]],"date-time":"2026-09-26T00:00:00Z","timestamp":1790380800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,9,26]],"date-time":"2026-09-26T00:00:00Z","timestamp":1790380800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,9,26]],"date-time":"2026-09-26T00:00:00Z","timestamp":1790380800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"name":"China West Normal University Horizontal Scientific Research Project","award":["KH2025-114"],"award-info":[{"award-number":["KH2025-114"]}],"id":[{"id":"https:\/\/ror.org\/04s99y476","id-type":"ROR","asserted-by":"crossref"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,10,8]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>The synthesis of unsaturated \u03b2-hydroxy nitriles is of significant importance in pharmaceutical and materials chemistry. However, traditional transition-metal-catalyzed reactions of \u03b1,\u03b2-unsaturated carbonyls often suffer from poor regioselectivity, favoring the thermodynamically controlled 1,4-addition over the desired 1,2-addition. To elucidate the origin of the high 1,2-regioselectivity observed experimentally in the Cu2O\/t-BuOK catalytic system, comprehensive density functional theory (DFT) calculations were performed using the M06-L-D3 functional with the ma-def2-TZVP basis set in the SMD solvation model. The computational results reveal that the reaction proceeds via a multistep mechanism involving ligand coordination, C\u2013H activation, and nucleophilic addition. The Hard\u2013Soft Acid\u2013Base (HSAB) theory and Dewar\u2013Chatt\u2013Duncanson (DCD) model confirm that the soft Cu(I) centers preferentially coordinate with the soft C\u2550C double bond of the aldehyde rather than the hard carbonyl oxygen. This coordination mode effectively polarizes the substrate, enhancing the electrophilicity of the carbonyl carbon and suppressing the competing 1,4-addition pathway. Among the identified pathways, the route via compound 11 is the most energetically favorable. The proton transfer assisted by t-BuO\u2013 exhibits an energy barrier of 16.5 kcal\/mol, leading to the formation of a nucleophilic cyanide anion. Subsequently, the energy barrier of 1,2-addition is 5.8 kcal\/mol lower than that of 1,4-addition, a preference attributed to stronger noncovalent interactions (NCIs) and shorter bond-forming distances in the transition state. This study provides deep mechanistic insights into the copper-catalyzed cyanomethylation of \u03b1,\u03b2-unsaturated aldehydes, highlighting the critical role of metal-substrate coordination geometry in controlling regioselectivity.<\/jats:p>","DOI":"10.1021\/acs.jpca.6c04564","type":"journal-article","created":{"date-parts":[[2026,9,26]],"date-time":"2026-09-26T15:02:10Z","timestamp":1790434930000},"page":"7942-7952","source":"Crossref","is-referenced-by-count":0,"title":["DFT Study on the\nOrigin of 1,2-Regioselectivity in\nCu2O-Catalyzed Addition of Acetonitrile to Cinnamaldehyde"],"prefix":"10.1021","volume":"130","author":[{"given":"Ye-Chuan","family":"Duan","sequence":"first","affiliation":[{"name":"China West Normal University , , ,","place":["Nanchong, China, 637002"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lu-Jia","family":"Zhong","sequence":"additional","affiliation":[{"name":"China West Normal University , , ,","place":["Nanchong, China, 637002"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bin","family":"Chen","sequence":"additional","affiliation":[{"name":"China West Normal University , , ,","place":["Nanchong, China, 637002"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2889-1349","authenticated-orcid":true,"given":"Da-Gang","family":"Zhou","sequence":"additional","affiliation":[{"name":"China West Normal University , , ,","place":["Nanchong, China, 637002"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,26]]},"reference":[{"issue":"13","key":"2026100809070754300_cit1","doi-asserted-by":"publisher","first-page":"2868","DOI":"10.1002\/cctc.201800509","article-title":"Oxa-Michael Addition\nto \u03b1,\u03b2-Unsaturated Nitriles: An Expedient Route to \u03b3-Amino\nAlcohols and Derivatives","volume":"10","author":"Guo","year":"2018","journal-title":"ChemCatchem"},{"issue":"8","key":"2026100809070754300_cit2","doi-asserted-by":"publisher","first-page":"4489","DOI":"10.1021\/acs.joc.7b00512","article-title":"DBU-Mediated\nDiastereoselective Aldol-Type Cyanomethylation of Isatins","volume":"82","author":"Rao","year":"2017","journal-title":"J. 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