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Mechanisms of Csp 3 ‐H or Nsp 2 ‐H functionalization of 2,3‐diaminoindoles with triplet O 2 : A density functional theory investigation
Author(s) -
Deng ZhePeng,
Zhou DaGang
Publication year - 2021
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.4134
Subject(s) - chemistry , density functional theory , intramolecular force , surface modification , molecule , computational chemistry , activation barrier , ring (chemistry) , stereochemistry , organic chemistry
The mechanisms of Csp 3 ‐H or Nsp 2 ‐H activations of 2,3‐diaminoindoles oxidized by triplet O 2 have been investigated with the method of M06‐2X‐D3/6‐31 + G(d,p) in the Universal Solvation Model Based on Solute Electron Density (SMD) model. The calculations indicate that the activation of 2,3‐diaminoindoles has three possible paths. First, the Csp 3 ‐H functionalization has a higher energy barrier than that of Nsp 2 ‐H activation; then an intramolecular H‐shift reaction happened to lose a H 2 O 2 molecule; the third step is a ring‐closure reaction and imidazolo‐indole skeleton would be constructed; finally, the elimination reaction occurred, and the final product would be yielded. Fukui function and dual descriptor could be used to predict the active sites of the reactants and intermediates. Results would provide valuable insights into these types of interactions and related ones.