1834-74-8Relevant articles and documents
Retraction: Harnessing Thiol as a Benzyl Reagent for Photocatalytic Reductive Benzylation of Imines (Organic Letters DOI: 10.1021/2Facs.orglett.0c00065)
Zhang, Jinghui,Zhang, Muliang
, p. 2112 - 2112 (2020)
The authors retract this article after finding in subsequent studies that the quality of the purchased catalysts has a notable impact on the reproducibility of the results. Accordingly, the authors note that additional work is necessary to understand the
Secondary amine compound synthesized from alkyne and synthesis method of secondary amine compound
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, (2018/10/19)
The invention relates to a secondary amine compound synthesized from alkyne and a synthesis method of the secondary amine compound. The specific structure of the compound is shown as the formula II inthe description. Meanwhile, the invention discloses the three-step one-pot synthesis method of the compound. According to the method, cheap and available acetenyl substituted benzene (I) is taken asa raw material. The method comprises steps as follows: step 1), fluorine-containing alcohol and water are taken as solvents and subjected to a hydration reaction under catalysis of trifluoromethanesulfonic acid, and an intermediate ketone is generated; step 2), aromatic amines are added directly to a reaction system, and imine is generated; step 3), tetrahydroxydiboron is added to the system, anda product II is obtained. No metal participates in the method, operation is simple and convenient, the raw materials are easily available, reaction conditions are mild, and yield is relatively high.
Palladium-catalyzed benzylic C-H benzylation via bis-benzylpalladium(II) complexes in water: An effective pathway for the direct construction of N-(1,2-diphenylethyl)anilines
Hikawa, Hidemasa,Izumi, Kyoko,Ino, Yukari,Kikkawa, Shoko,Yokoyama, Yuusaku,Azumaya, Isao
, p. 1037 - 1048 (2015/03/30)
A strategy for the N-benzylation/benzylic C-H benzylation cascade of anilines by the π-benzylpalladium system using a water-soluble palladium(0)/sodium diphenylphosphinobenzene-3-sulfonate (TPPMS) catalyst and benzyl alcohol in water has been developed. This tandem process is devised as a novel and efficient synthetic route for N-(1,2-diphenylethyl)anilines. Benzylic C-H activation of a mono-N-benzylated intermediate with a π-benzylpalladium(II) complex affords a bis-π-benzylated palladium(II) intermediate. The nucleophilic η1-σ-benzyl anion ligand attacks the electrophilic η3-π-benzyl ligand to give a dibenzylated product. The intermolecular competition between mono-N-benzylaniline and its monodeuterated form (monodeuterated at the benzylic group) with benzyl alcohol gave a KIE=4.6, suggesting that C-H bond cleavage was involved in the rate-determining step. Hammett studies on the rate constants of benzylation by various substituted anthranilic acids and mono-N-benzylanilines show a good correlation between the log(kX/kH) and the σ values of the respective substituents. From the slope, negative ρ values are obtained, suggesting that there is a build-up of positive charge in the transition state. The reaction of anilines with electron-donating and electron-withdrawing groups affords the corresponding N-(1,2-diphenylethyl)anilines in moderate to good yields (54-86%). Interestingly, the reaction of anthranilic acids proceeded smoothly to give only the corresponding dibenzylated products in good to excellent yields (70-87%). The carboxyl group of the anthranilic acids acts as a directing group in the benzylic C-H activation process.
