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Density Functional Theory Mechanistic Study of Boron‐Catalyzed N‐Alkylation of Amines with Formic Acid: Formic Acid Activation by Silylation Reaction
Author(s) -
Du Pan,
Zhao Jiyang
Publication year - 2018
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201701607
Subject(s) - formic acid , alkylation , chemistry , electrophile , nucleophile , silylation , catalysis , lewis acids and bases , brønsted–lowry acid–base theory , reaction mechanism , amine gas treating , medicinal chemistry , organic chemistry
New methodology for the alkylation of amines is an intriguing issue in both academia and industry. Recently, several groups reported the metal‐free B(C 6 F 5 ) 3 ‐catalyzed N‐alkylation of amines, but the mechanistic details of these important reactions are unclear. Herein, a computational study was performed to elucidate the mechanism of the N‐alkylation of amines with formic acid catalyzed by the Lewis acid B(C 6 F 5 ) 3 in the presence of hydrosilane. We found that the reaction started with the activation of formic acid through a novel model. Then, the high electrophilicity of the C center of the formic acid unit and the nucleophilic character of the amine resulted in a C−N coupling reaction. Finally, two sequential silyl‐group and H − transfer steps occurred to generate the final product. Upon comparing the reaction barrier and the hydrogenation of indole, our mechanism is more favorable than that proposed by the group of Yu and Fu.