Matches in SemOpenAlex for { <https://semopenalex.org/work/W2773618806> ?p ?o ?g. }
- W2773618806 endingPage "570" @default.
- W2773618806 startingPage "561" @default.
- W2773618806 abstract "The recent Cu-catalyzed allylic substitution reaction between gem-diboryalkane and allyl electrophiles shows intriguing solvent and ligand-controlled regioselectivity. The α-alkylation product was obtained in DMF solvent, while γ-alkylation product was obtained in dioxane solvent and the dioxane and NHC ligand situation. In the present study, density functional theory calculations have been used to investigate the reaction mechanism and origin of the regioselectivity. For both dioxane and DMF, γ-alkylation undergoes successive oxidative addition (CH2Bpin trans to leaving group) and direct Cγ–C reductive elimination. The α-alkylation is found to undergo oxidative addition (CH2Bpin trans to leaving group), isomerization, and Cα–C reductive elimination rather than the previously proposed oxidative addition (−CH2Bpin cis to the leaving group) and Cα–C reductive elimination. The γ-alkylation and α-alkylation is, respectively, favorable for dioxane and DMF solvent, which is consistent with the γ- and α-selectivity in experiment. The solvent interferes the isomerization step, thereby affects the relative facility of the α- and γ-alkylation. Further investigation shows that η1-intermediate formation promoted by solvent is the rate-determining step of the isomerization. The stronger electron-donating ability of DMF than dioxane facilitates the η1-intermediate formation and finally results in the easier isomerization in DMF. For dioxane and NHC situation, in the presence of neutral NHC ligand, the −PO4Et2 group tightly coordinates with the Cu center after the oxidative addition, preventing the isomerization process. The regioselectivity is determined by the relative facility of the oxidative addition step. Therefore, the favorable oxidative addition (in which −CH2Bpin trans to the leaving group) results in the facility of γ-alkylation." @default.
- W2773618806 created "2017-12-22" @default.
- W2773618806 creator A5026984704 @default.
- W2773618806 creator A5030892786 @default.
- W2773618806 creator A5039970749 @default.
- W2773618806 creator A5040040696 @default.
- W2773618806 creator A5058599098 @default.
- W2773618806 date "2017-12-28" @default.
- W2773618806 modified "2023-10-14" @default.
- W2773618806 title "Mechanistic Insights into Solvent and Ligand Dependency in Cu(I)-Catalyzed Allylic Alkylation with <i>gem</i>-Diborylalkanes" @default.
- W2773618806 cites W1963997589 @default.
- W2773618806 cites W1964837435 @default.
- W2773618806 cites W1967993282 @default.
- W2773618806 cites W1974660623 @default.
- W2773618806 cites W1978890358 @default.
- W2773618806 cites W1999369741 @default.
- W2773618806 cites W2003782193 @default.
- W2773618806 cites W2008243011 @default.
- W2773618806 cites W2012827252 @default.
- W2773618806 cites W2018886758 @default.
- W2773618806 cites W2023167754 @default.
- W2773618806 cites W2023271753 @default.
- W2773618806 cites W2027797878 @default.
- W2773618806 cites W2032065441 @default.
- W2773618806 cites W2047109196 @default.
- W2773618806 cites W2050690270 @default.
- W2773618806 cites W2055258517 @default.
- W2773618806 cites W2064259630 @default.
- W2773618806 cites W2065813156 @default.
- W2773618806 cites W2066722622 @default.
- W2773618806 cites W2075932575 @default.
- W2773618806 cites W2079458939 @default.
- W2773618806 cites W2082712943 @default.
- W2773618806 cites W2085336624 @default.
- W2773618806 cites W2091567820 @default.
- W2773618806 cites W2098482820 @default.
- W2773618806 cites W2099341182 @default.
- W2773618806 cites W2111741771 @default.
- W2773618806 cites W2124746699 @default.
- W2773618806 cites W2125689057 @default.
- W2773618806 cites W2132673906 @default.
- W2773618806 cites W2135442302 @default.
- W2773618806 cites W2137067149 @default.
- W2773618806 cites W2143981217 @default.
- W2773618806 cites W2150697053 @default.
- W2773618806 cites W2161550840 @default.
- W2773618806 cites W2221280590 @default.
- W2773618806 cites W2256161425 @default.
- W2773618806 cites W2270025540 @default.
- W2773618806 cites W2310290166 @default.
- W2773618806 cites W2314567142 @default.
- W2773618806 cites W2319029112 @default.
- W2773618806 cites W2319116898 @default.
- W2773618806 cites W2323695100 @default.
- W2773618806 cites W2324691338 @default.
- W2773618806 cites W2326506138 @default.
- W2773618806 cites W2328482668 @default.
- W2773618806 cites W2334349361 @default.
- W2773618806 cites W2506986136 @default.
- W2773618806 cites W2514872918 @default.
- W2773618806 cites W2613566661 @default.
- W2773618806 cites W4231507874 @default.
- W2773618806 cites W4367275817 @default.
- W2773618806 doi "https://doi.org/10.1021/acs.joc.7b02249" @default.
- W2773618806 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/29244488" @default.
- W2773618806 hasPublicationYear "2017" @default.
- W2773618806 type Work @default.
- W2773618806 sameAs 2773618806 @default.
- W2773618806 citedByCount "12" @default.
- W2773618806 countsByYear W27736188062018 @default.
- W2773618806 countsByYear W27736188062019 @default.
- W2773618806 countsByYear W27736188062021 @default.
- W2773618806 countsByYear W27736188062023 @default.
- W2773618806 crossrefType "journal-article" @default.
- W2773618806 hasAuthorship W2773618806A5026984704 @default.
- W2773618806 hasAuthorship W2773618806A5030892786 @default.
- W2773618806 hasAuthorship W2773618806A5039970749 @default.
- W2773618806 hasAuthorship W2773618806A5040040696 @default.
- W2773618806 hasAuthorship W2773618806A5058599098 @default.
- W2773618806 hasConcept C116569031 @default.
- W2773618806 hasConcept C120095180 @default.
- W2773618806 hasConcept C126661725 @default.
- W2773618806 hasConcept C155647269 @default.
- W2773618806 hasConcept C160964918 @default.
- W2773618806 hasConcept C161790260 @default.
- W2773618806 hasConcept C164361826 @default.
- W2773618806 hasConcept C170493617 @default.
- W2773618806 hasConcept C178790620 @default.
- W2773618806 hasConcept C185592680 @default.
- W2773618806 hasConcept C27083343 @default.
- W2773618806 hasConcept C2778815869 @default.
- W2773618806 hasConcept C2780471494 @default.
- W2773618806 hasConcept C50027330 @default.
- W2773618806 hasConcept C55493867 @default.
- W2773618806 hasConcept C59759590 @default.
- W2773618806 hasConcept C75473681 @default.
- W2773618806 hasConcept C94882840 @default.
- W2773618806 hasConceptScore W2773618806C116569031 @default.