Premium
Iodotriflamdation vs. Electrophilic Aromatic Iodination in the Reaction of N‐Phenyltriflamide with Alkenes
Author(s) -
Astakhova Vera V.,
Moskalik Mikhail Yu.,
Ganin Anton S.,
Sterkhova Irina V.,
Shainyan Bagrat A.
Publication year - 2018
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201801379
Subject(s) - halogenation , regioselectivity , chemistry , electrophile , medicinal chemistry , electrophilic addition , electrophilic aromatic substitution , benzene , reagent , electrophilic substitution , organic chemistry , catalysis
Reaction of N‐phenyltriflamide with styrene, p‐chlorostyrene, vinylcyclohexane and α‐methylstyrene in oxidative system (t‐BuOCl + NaI) gives three types of products: (i) of aromatic iodination of the reagent – N‐(4‐iodophenyl)triflamide and N‐(2,4‐diiodophenyl)triflamide; (ii) of oxidative addition of the iodinated reagent to the substrate with different regioselectivity – N‐[2‐iodo‐1‐(aryl)ethyl]‐N‐(4‐iodophenyl)triflamides or N‐(2‐cyclohexyl‐2‐iodoethyl)‐N‐(4‐iodophenyl)triflamide; (iii) of chloro(oxy)iodination of the substrate – 2‐iodo‐1‐phenylethanol, 1‐chloro‐4‐(1‐chloro‐2‐iodoethyl)benzene, 1‐cyclohexyl‐2‐iodoethanol and 1‐iodo‐2‐phenylpropan‐2‐ol. Different regioselectivity of iodosulfonamidation for different alkenes and the competition between electrophilic aromatic iodination and iodotriflamidation are explained and the mechanism is proposed based on the results of quantum chemical calculations and the NBO analysis.