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• W2771060306 endingPage "13050" @default.
• W2771060306 startingPage "13043" @default.
• W2771060306 abstract "The N-heterocyclic carbene (NHC)-catalyzed γ-C–H deprotonation/functionalization of α,β-unsaturated esters with hydrazones leading to the δ-lactams has been theoretically investigated by using density functional theory. Three possible reaction mechanisms including Mechanism A, for which the NHC catalyst serves as a nucleophilic catalyst to attack on the carbonyl carbon atom to initiate the reaction, Mechanism B, in which NHC triggers the reaction through the hydrogen bond, and Mechanism C, which is the direct deprotonation/functionalization process without the presence of NHC, have been suggested and studied in detail. The most favorable Mechanism A was identified to proceed through the following processes: nucleophilic attack on the carbonyl carbon of the ester by NHC, γ-deprotonation, formal [4 + 2] cycloaddition of dienolate with hydrazone, and regeneration of NHC. Multiple possible deprotonation pathways were explored, and the additive base such as K2CO3 would significantly lower the energy barrier. The formal [4 + 2] cycloaddition step is the stereoselectivity-determining step, and R-configured rather than S-configured product was preferentially generated. In addition, the C–H···O, C–H···N, LP···π, and C–H···π interactions have been identified in the most energetically favorable transition state involved in the stereoselectivity-determining step. The additional analysis indicates that NHC strengthens the acidity and electrophilicity to promote the deprotonation, indicating this is not a simple NHC-catalyzed umpolung carbonyl reaction. The mechanistic insights and the significant role of NHC obtained in this study should provide valuable insights for understanding the organocatalytic γ-C(sp3)–H bond functionalization reaction." @default.
• W2771060306 created "2017-12-04" @default.
• W2771060306 creator A5041300808 @default.
• W2771060306 creator A5049662454 @default.
• W2771060306 creator A5071296084 @default.
• W2771060306 date "2017-11-22" @default.
• W2771060306 modified "2023-10-17" @default.
• W2771060306 title "Computational Study on γ-C–H Functionalization of α,β-Unsaturated Ester Catalyzed by N-Heterocyclic Carbene: Mechanisms, Origin of Stereoselectivity, and Role of Catalyst" @default.
• W2771060306 cites W1714804572 @default.
• W2771060306 cites W1792914280 @default.
• W2771060306 cites W1880495637 @default.
• W2771060306 cites W1980449730 @default.
• W2771060306 cites W1981088034 @default.
• W2771060306 cites W1982928176 @default.
• W2771060306 cites W1984599229 @default.
• W2771060306 cites W1987894799 @default.
• W2771060306 cites W1990994141 @default.
• W2771060306 cites W1992728909 @default.
• W2771060306 cites W1992951420 @default.
• W2771060306 cites W1994390276 @default.
• W2771060306 cites W1999257584 @default.
• W2771060306 cites W2003240060 @default.
• W2771060306 cites W2003555872 @default.
• W2771060306 cites W2008648562 @default.
• W2771060306 cites W2011195486 @default.
• W2771060306 cites W2012945226 @default.
• W2771060306 cites W2014767176 @default.
• W2771060306 cites W2016244145 @default.
• W2771060306 cites W2023684236 @default.
• W2771060306 cites W2027737429 @default.
• W2771060306 cites W2034764833 @default.
• W2771060306 cites W2038092103 @default.
• W2771060306 cites W2047564730 @default.
• W2771060306 cites W2050404939 @default.
• W2771060306 cites W2051475170 @default.
• W2771060306 cites W2052208234 @default.
• W2771060306 cites W2059952765 @default.
• W2771060306 cites W2064969177 @default.
• W2771060306 cites W2070096324 @default.
• W2771060306 cites W2074952873 @default.
• W2771060306 cites W2079180580 @default.
• W2771060306 cites W2079458939 @default.
• W2771060306 cites W2085336624 @default.
• W2771060306 cites W2085966856 @default.
• W2771060306 cites W2097129068 @default.
• W2771060306 cites W2098666555 @default.
• W2771060306 cites W2101264446 @default.
• W2771060306 cites W2107167062 @default.
• W2771060306 cites W2107779849 @default.
• W2771060306 cites W2126001191 @default.
• W2771060306 cites W2132525235 @default.
• W2771060306 cites W2147355442 @default.
• W2771060306 cites W2150553038 @default.
• W2771060306 cites W2150697053 @default.
• W2771060306 cites W2159210084 @default.
• W2771060306 cites W2162543215 @default.
• W2771060306 cites W2162846787 @default.
• W2771060306 cites W2167299139 @default.
• W2771060306 cites W2173330079 @default.
• W2771060306 cites W2201027473 @default.
• W2771060306 cites W2237269708 @default.
• W2771060306 cites W2239429815 @default.
• W2771060306 cites W2243221203 @default.
• W2771060306 cites W2253045979 @default.
• W2771060306 cites W2261068668 @default.
• W2771060306 cites W2299637886 @default.
• W2771060306 cites W2315874011 @default.
• W2771060306 cites W2319992633 @default.
• W2771060306 cites W2322474591 @default.
• W2771060306 cites W2326598733 @default.
• W2771060306 cites W2330309804 @default.
• W2771060306 cites W2330793203 @default.
• W2771060306 cites W2345159345 @default.
• W2771060306 cites W2399074341 @default.
• W2771060306 cites W2409881175 @default.
• W2771060306 cites W2417861041 @default.
• W2771060306 cites W2460521252 @default.
• W2771060306 cites W2465328398 @default.
• W2771060306 cites W2472317335 @default.
• W2771060306 cites W2496920787 @default.
• W2771060306 cites W2507261765 @default.
• W2771060306 cites W2526402393 @default.
• W2771060306 cites W2532527353 @default.
• W2771060306 cites W2553905046 @default.
• W2771060306 cites W2560332697 @default.
• W2771060306 cites W2598938866 @default.
• W2771060306 cites W2619459099 @default.
• W2771060306 cites W2625904587 @default.
• W2771060306 cites W2730927833 @default.
• W2771060306 cites W2752262507 @default.
• W2771060306 cites W2950547160 @default.
• W2771060306 cites W4232619580 @default.
• W2771060306 cites W4240532892 @default.
• W2771060306 cites W4247561711 @default.
• W2771060306 cites W4376848409 @default.
• W2771060306 doi "https://doi.org/10.1021/acs.joc.7b01992" @default.
• W2771060306 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/29135242" @default.
• W2771060306 hasPublicationYear "2017" @default.

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