In 2018,Zhang, Qi; Wang, Bing; Liu, Jia-Qin; Fu, Yao; Wu, Yu-Cheng published 《Mechanistic Insights into Solvent and Ligand Dependency in Cu(I)-Catalyzed Allylic Alkylation with gem-Diborylalkanes》.Journal of Organic Chemistry published the findings.Related Products of 78782-17-9 The information in the text is summarized as follows:
The recent Cu-catalyzed allylic substitution reaction between gem-diborylalkane 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, d. 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, resp., 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.Bis[(pinacolato)boryl]methane(cas: 78782-17-9Related Products of 78782-17-9) was used in this study.
Bis[(pinacolato)boryl]methane(cas: 78782-17-9) belongs to organoboron compounds. Organoboron compounds have been a cornerstone of synthetic transformations for decades. Areas such as boron-containing catalysts, metalate chemistry, photoredox methods, and boryl anions have brought significant new developments in understanding and provided new reactivity upon.Related Products of 78782-17-9
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