Monoalkylation of aniline with trichloroacetimidate catalyzed by (±)-camphorsulfonic acid through an S1 reaction based on dual hydrogen-bonding activation modes
Monoalkylation of aniline can be readily achieved using trichloroacetimidate as an alkylating agent and a Brønsted acid, such as (±)-camphorsulfonic acid, as a catalyst. In this study, systematic theoretical calculations were performed to understand the reaction mechanism for the monoalkylation of 2...
Saved in:
Published in | New journal of chemistry Vol. 44; no. 14; pp. 5526 - 5534 |
---|---|
Main Authors | , , , , , , |
Format | Journal Article |
Language | English |
Published |
06.04.2020
|
Online Access | Get full text |
Cover
Loading…
Summary: | Monoalkylation of aniline can be readily achieved using trichloroacetimidate as an alkylating agent and a Brønsted acid, such as (±)-camphorsulfonic acid, as a catalyst. In this study, systematic theoretical calculations were performed to understand the reaction mechanism for the monoalkylation of 2,5-dichloroaniline with trichloroacetimidate catalyzed by (±)-camphorsulfonic acid; moreover, the judgement about whether the reaction takes place
via
an S
N
1 or S
N
2 mechanism was elaborated. The two possible proton-transfer reaction mechanisms proposed herein based on the experimental results were investigated; moreover, another two possible reaction mechanisms involving the activation of both 2,5-dichloroaniline and trichloroacetimidate by (±)-camphorsulfonic acid
via
dual hydrogen-bonding activation modes were evaluated. The calculated results suggest that the reaction between 2,5-dichloroaniline and trichloroacetimidate catalyzed by (±)-camphorsulfonic acid preferentially occurs through the S
N
1 mechanism based on the dual hydrogen-bonding activation modes.
Herein, the monoalkylation of anilines with trichloroacetimidates catalyzed by CSA was investigated theoretically, and it was found that the reaction occurred through an S
N
1 reaction involving the dual hydrogen-bonding activation modes. |
---|---|
Bibliography: | Electronic supplementary information (ESI) available: QTAIM analyses of the complexes, transition states, and intermediates. The Cartesian coordinates for the optimized reactants, catalysts, complexes, transition states, intermediates, and products obtained at the M06-2×/6-31G(d,p) level of theory. See DOI 10.1039/d0nj00239a |
ISSN: | 1144-0546 1369-9261 |
DOI: | 10.1039/d0nj00239a |