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Here, we present a systematic benchmark of DFT exchange\u2013correlation functional\/basis-set combinations against CCSD(T) reference energies for the thermal Conia\u2013Ene cyclization, using chain length and explicit water assistance as chemically relevant probes of functional performance. Representative reaction profiles were constructed for two model substrates (hex-5-ynal and hept-6-ynal), considering pathways with and without explicit water, in both gas phase and implicit solvent. The reaction proceeds stepwise through enolization followed by cyclization, with enolization defining the intrinsic kinetic bottleneck in the water-free pathway (ca. 70 kcal mol\u20131). Explicit water selectively lowers this barrier by up to 30 kcal mol\u20131 through proton-transfer mediation, whereas the cyclization barrier is primarily controlled by chain length through transition-state preorganization; implicit solvation has only a minor energetic effect. Across 38 approximate exchange\u2013correlation functionals and 14 basis sets, range-separated hybrids provide the most accurate and balanced description of both activation barriers and reaction energies. In particular, \u03c9B97XD and CAM-B3LYP-D3BJ achieve near-chemical accuracy, with mean absolute errors close to 1 kcal mol\u20131 when combined with triple-\u03b6 basis sets containing polarization and diffuse functions. Comparable accuracy is also achieved by the double-hybrid functionals mPW2PLYP and DSD-PBEP86, albeit at a substantially higher computational cost. Overall, this study establishes a practical CCSD(T)-referenced benchmark and identifies robust DFT protocols for modeling thermal Conia\u2013Ene cyclizations, with expected transferability to more complex substrates and confined environments.<\/jats:p>","DOI":"10.1021\/acsomega.6c05834","type":"journal-article","created":{"date-parts":[[2026,8,18]],"date-time":"2026-08-18T20:02:06Z","timestamp":1787083326000},"page":"51623-51634","source":"Crossref","is-referenced-by-count":0,"title":["Benchmarking DFT\nfor Chain-Length and Water Effects\nin Thermal Conia\u2013Ene Cyclization"],"prefix":"10.1021","volume":"11","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0549-7744","authenticated-orcid":true,"given":"Jorge","family":"Gutie\u0301rrez-Flores","sequence":"first","affiliation":[{"name":"Universidad Auto\u0301noma Metropolitana Iztapalapa , , San Rafael Atlixco 186, Col. Vicentina , Iztapalapa, ,","place":["Ciudad de Me\u0301xico, Me\u0301xico, C.P. 09340"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4883-4528","authenticated-orcid":true,"given":"Eduardo","family":"H. Huerta","sequence":"additional","affiliation":[{"name":"Instituto de Qui\u0301mica, Circuito Exterior, Ciudad Universitaria , , Alc. Coyoaca\u0301n , ,","place":["Ciudad de Me\u0301xico, Me\u0301xico, 04510"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Javier","family":"Serrano Medina","sequence":"additional","affiliation":[{"name":"Universidad Auto\u0301noma Metropolitana Iztapalapa , , San Rafael Atlixco 186, Col. Vicentina , Iztapalapa, ,","place":["Ciudad de Me\u0301xico, Me\u0301xico, C.P. 09340"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jorge","family":"Garza","sequence":"additional","affiliation":[{"name":"Universidad Auto\u0301noma Metropolitana Iztapalapa , , San Rafael Atlixco 186, Col. Vicentina , Iztapalapa, ,","place":["Ciudad de Me\u0301xico, Me\u0301xico, C.P. 09340"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8686-160X","authenticated-orcid":true,"given":"Marcos","family":"Herna\u0301ndez-Rodriguez","sequence":"additional","affiliation":[{"name":"Instituto de Qui\u0301mica, Circuito Exterior, Ciudad Universitaria , , Alc. 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Lett."},{"key":"2026090307201002300_cit5","doi-asserted-by":"publisher","first-page":"2219","DOI":"10.1039\/d5ob01665g","article-title":"A gold(iii)-catalyzed\nConia-ene reaction\nfor the direct synthesis of substituted pyrroles from \u03b2-ketopropargyl amines","volume":"24","author":"Badr","year":"2026","journal-title":"Org. Biomol. Chem."},{"key":"2026090307201002300_cit6","doi-asserted-by":"publisher","first-page":"217","DOI":"10.1351\/PAC-CON-08-07-14","article-title":"Indium-catalyzed\nConia-ene reaction for alkaloid synthesis","volume":"81","author":"Hatakeyama","year":"2009","journal-title":"Pure\nAppl. Chem."},{"key":"2026090307201002300_cit7","doi-asserted-by":"publisher","first-page":"1045","DOI":"10.1248\/cpb.c14-00474","article-title":"Total Synthesis\nof Biologically Active Natural Products Based on Highly Selective\nSynthetic Methodologies","volume":"62","author":"Hatakeyama","year":"2014","journal-title":"Chem. Pharm. 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Chem."},{"key":"2026090307201002300_cit22","doi-asserted-by":"publisher","first-page":"4637","DOI":"10.1021\/ct300329h","article-title":"Effects\nof Dispersion in Density\nFunctional Based Quantum Mechanical\/Molecular Mechanical Calculations\non Cytochrome P450 Catalyzed Reactions","volume":"8","author":"Lonsdale","year":"2012","journal-title":"J. Chem.\nTheory Comput."},{"key":"2026090307201002300_cit23","doi-asserted-by":"publisher","first-page":"805","DOI":"10.1021\/om501199t","article-title":"Dispersion\nMakes the Difference:\nBisligated Transition States Found for the Oxidative Addition of Pd(P\nt Bu3)2 to Ar-OSO2 R and Dispersion-Controlled\nChemoselectivity in Reactions with Pd[P(i Pr)(t Bu2)]2","volume":"34","author":"Lyngvi","year":"2015","journal-title":"Organometallics"},{"issue":"49","key":"2026090307201002300_cit24","doi-asserted-by":"publisher","first-page":"20837","DOI":"10.1021\/jacs.1c09222","article-title":"London\ndispersion helps refine steric\na-values: Dispersion energy donor scales","volume":"143","author":"Solel","year":"2021","journal-title":"J.\nAm. Chem. 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Lett."},{"issue":"10","key":"2026090307201002300_cit46","doi-asserted-by":"publisher","first-page":"5978","DOI":"10.1021\/acs.jctc.2c00426","article-title":"Explicitly Correlated\nDouble-Hybrid DFT: A Comprehensive\nAnalysis of the Basis Set Convergence on the GMTKN55 Database","volume":"18","author":"Mehta","year":"2022","journal-title":"J. Chem. Theory Comput."},{"issue":"2","key":"2026090307201002300_cit47","doi-asserted-by":"publisher","DOI":"10.1063\/5.0011674","article-title":"Effective\nbasis set extrapolations for CCSDT, CCSDT(Q), and CCSDTQ correlation\nenergies","volume":"153","author":"Karton","year":"2020","journal-title":"J. Chem. Phys.,"},{"key":"2026090307201002300_cit48","doi-asserted-by":"publisher","first-page":"3865","DOI":"10.1103\/PhysRevLett.77.3865","article-title":"Generalized Gradient Approximation\nMade Simple","volume":"77","author":"Perdew","year":"1996","journal-title":"Phys. Rev. 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