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Mechanistic study on silver(I)‐catalyzed aminofluorination of unactivated alkenes
Author(s) -
Zhang Xiang
Publication year - 2017
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3655
Subject(s) - chemistry , selectfluor , deprotonation , intramolecular force , homolysis , regioselectivity , catalytic cycle , catalysis , bond cleavage , medicinal chemistry , amide , photochemistry , radical , organic chemistry , ion
A study has been performed on the mechanism for the Ag(I)‐catalyzed intramolecular aminofluorination of N ‐arylpent‐4‐enamides with Selectfluor by means of density functional theory. According to the calculations, the whole catalytic cycle consists of a series of elementary reactions, including formation of the complex ( IMC ) of the substrate and Ag(H 2 O) + (derived from the ligation of H 2 O to Ag(I)), oxidation of the complex IMC by Selectfluor, deprotonation, homolytic cleavage of the N–Ag(II) bond, intramolecular radical cyclization, and fluorine abstraction. It is suggested that the oxidation of the complex IMC should be the rate‐determining step and that the intramolecular radical cyclization determines the regioselectivity of the reaction. Different from that in the decarboxylative fluorination, herein, the deprotonation of the amide is initiated by Ag(II) rather than Ag(I).