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Superelectrophilic Activation of N ‐Substituted Isatins: Implications for Polymer Synthesis, a Theoretical Study
Author(s) -
Nieto Daniel Romero,
Fomine Serguei,
Zolotukhin Mikhail G.,
Fomina Lioudmila,
Hernandez Maria del Carmen Gutiérrez
Publication year - 2009
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/mats.200800075
Subject(s) - isatin , electrophile , reactivity (psychology) , steric effects , chemistry , triflic acid , computational chemistry , combinatorial chemistry , organic chemistry , medicinal chemistry , catalysis , medicine , alternative medicine , pathology
The stability and reactivity of mono‐ and multi‐protonatred N ‐substituted isatin derivatives were studied at PBE0/aug‐cc‐pvtz//PBE0/6‐31+G** level of theory in triflic acid (TFSA) solution. Calculations showed that the monocationic intermediates are the principal reactive species in the reaction of hydroxyalkylation of isatin derivatives in TFSA media. Electron‐withdrawing substituents on the nitrogen atom increase the reactivity of isatin‐containing electrophiles towards aromatic hydrocarbons, in accordance with their expected electronic influence. Steric factors also play an important role in the reactivity of isatin‐containing electrophiles, especially in the second reaction step, due to their more sterically hindered reactive center.