FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2040556616> ?p ?o ?g. }

• W2040556616 endingPage "5081" @default.
• W2040556616 startingPage "5074" @default.
• W2040556616 abstract "CBS-QB3 enthalpies of reaction have been computed for the conjugate additions of MeSH to six α,β-unsaturated ketones. Compared with addition to methyl vinyl ketone, the reaction becomes 1–3 kcal mol–1 less exothermic when an α-Me, β-Me, or β-Ph substituent is present on the C═C bond. The lower exothermicity for the substituted enones occurs because the substituted reactant is stabilized more by hyperconjugation or conjugation than the product is stabilized by branching. Substituent effects on the activation energies for the rate-determining step of the thiol addition (reaction of the enone with MeS–) were also computed. Loss of reactant stabilization, and not steric hindrance, is the main factor responsible for controlling the relative activation energies in the gas phase. The substituent effects are further magnified in solution; in water (simulated by CPCM calculations), the addition of MeS– to an enone is disfavored by 2–6 kcal mol–1 when one or two methyl groups are present on the C═C bond (ΔΔG⧧). The use of CBS-QB3 gas-phase energies in conjunction with CPCM solvation corrections provides kinetic data in good agreement with experimental substituent effects. When the energetics of the thiol additions were calculated with several popular density functional theory and ab initio methods (B3LYP, MPW1PW91, B1B95, PBE0, B2PLYP, and MP2), some substantial inaccuracies were noted. However, M06-2X (with a large basis set), B2PLYP-D, and SCS-MP2 gave results within 1 kcal mol–1 of the CBS-QB3 benchmark values." @default.
• W2040556616 created "2016-06-24" @default.
• W2040556616 creator A5000188305 @default.
• W2040556616 creator A5012261150 @default.
• W2040556616 creator A5042178740 @default.
• W2040556616 creator A5043971328 @default.
• W2040556616 date "2011-05-16" @default.
• W2040556616 modified "2023-10-18" @default.
• W2040556616 title "Transition States and Energetics of Nucleophilic Additions of Thiols to Substituted α,β-Unsaturated Ketones: Substituent Effects Involve Enone Stabilization, Product Branching, and Solvation" @default.
• W2040556616 cites W180207602 @default.
• W2040556616 cites W1809679124 @default.
• W2040556616 cites W1963895146 @default.
• W2040556616 cites W1966544292 @default.
• W2040556616 cites W1975885494 @default.
• W2040556616 cites W1978854006 @default.
• W2040556616 cites W1981368803 @default.
• W2040556616 cites W1982356449 @default.
• W2040556616 cites W1983586491 @default.
• W2040556616 cites W1983656816 @default.
• W2040556616 cites W1984075743 @default.
• W2040556616 cites W1987702006 @default.
• W2040556616 cites W1994372519 @default.
• W2040556616 cites W1995792670 @default.
• W2040556616 cites W1997122475 @default.
• W2040556616 cites W2003691545 @default.
• W2040556616 cites W2004521864 @default.
• W2040556616 cites W2006672210 @default.
• W2040556616 cites W2008423326 @default.
• W2040556616 cites W2010993054 @default.
• W2040556616 cites W2014767176 @default.
• W2040556616 cites W2017488631 @default.
• W2040556616 cites W2019216438 @default.
• W2040556616 cites W2022558488 @default.
• W2040556616 cites W2023271753 @default.
• W2040556616 cites W2036319937 @default.
• W2040556616 cites W2038417897 @default.
• W2040556616 cites W2040195084 @default.
• W2040556616 cites W2040916569 @default.
• W2040556616 cites W2041587408 @default.
• W2040556616 cites W2051065931 @default.
• W2040556616 cites W2054118324 @default.
• W2040556616 cites W2057815662 @default.
• W2040556616 cites W2058668246 @default.
• W2040556616 cites W2058848030 @default.
• W2040556616 cites W2060060992 @default.
• W2040556616 cites W2062482627 @default.
• W2040556616 cites W2063918193 @default.
• W2040556616 cites W2065159255 @default.
• W2040556616 cites W2067313316 @default.
• W2040556616 cites W2070203126 @default.
• W2040556616 cites W2077804275 @default.
• W2040556616 cites W2079458939 @default.
• W2040556616 cites W2082917109 @default.
• W2040556616 cites W2085980720 @default.
• W2040556616 cites W2086505034 @default.
• W2040556616 cites W2086780048 @default.
• W2040556616 cites W2087902760 @default.
• W2040556616 cites W2092836350 @default.
• W2040556616 cites W2095100262 @default.
• W2040556616 cites W2098985212 @default.
• W2040556616 cites W2099629334 @default.
• W2040556616 cites W2101044792 @default.
• W2040556616 cites W2102019455 @default.
• W2040556616 cites W2103176800 @default.
• W2040556616 cites W2108608653 @default.
• W2040556616 cites W2117894566 @default.
• W2040556616 cites W2128495272 @default.
• W2040556616 cites W2130029082 @default.
• W2040556616 cites W2131588456 @default.
• W2040556616 cites W2135249818 @default.
• W2040556616 cites W2143981217 @default.
• W2040556616 cites W2149952977 @default.
• W2040556616 cites W2150202960 @default.
• W2040556616 cites W2150697053 @default.
• W2040556616 cites W2153156618 @default.
• W2040556616 cites W2169479751 @default.
• W2040556616 cites W2317012207 @default.
• W2040556616 cites W2319706965 @default.
• W2040556616 cites W2322773730 @default.
• W2040556616 cites W2324603767 @default.
• W2040556616 cites W2326202062 @default.
• W2040556616 cites W2949357325 @default.
• W2040556616 cites W2949533572 @default.
• W2040556616 cites W2949648363 @default.
• W2040556616 cites W2950462857 @default.
• W2040556616 cites W2950606388 @default.
• W2040556616 cites W2950679622 @default.
• W2040556616 cites W2951943334 @default.
• W2040556616 cites W3150291107 @default.
• W2040556616 cites W3206606417 @default.
• W2040556616 doi "https://doi.org/10.1021/jo200761w" @default.
• W2040556616 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/21574592" @default.
• W2040556616 hasPublicationYear "2011" @default.
• W2040556616 type Work @default.
• W2040556616 sameAs 2040556616 @default.
• W2040556616 citedByCount "80" @default.
• W2040556616 countsByYear W20405566162012 @default.
• W2040556616 countsByYear W20405566162013 @default.

• next