Theoretical Study on the Mechanism of Rearrangement
Reactions of Bicyclic Derivatives of Cyclopropane to Monocyclic Derivatives
under the Catalysis of Pt-Salt
Arpita Chatterjee
Sonjoy Mondal
Rohini Saha
Poulami Pal
Kuheli Chakrabarty
Gourab Kanti Das
10.1021/acsomega.8b02344.s001
https://acs.figshare.com/articles/journal_contribution/Theoretical_Study_on_the_Mechanism_of_Rearrangement_Reactions_of_Bicyclic_Derivatives_of_Cyclopropane_to_Monocyclic_Derivatives_under_the_Catalysis_of_Pt-Salt/7396712
In this paper, the
mechanistic studies on the isomerization of
hydroxyl and silyl derivatives of bicyclic cyclopropanes under the
catalytic action of Zeise’s salt have been reported. The catalytic
activity of both the monomeric and the dimeric forms of Zeise’s
salt has been studied by applying the high-level quantum mechanical
method. Results from this investigation reveal that the reaction goes
favorably under the catalysis of the dimeric form of Zeise’s
salt. The calculated activation barrier for the catalytic process
using Zeise’s dimer reveals that the rearrangement occurs with
an activation barrier of 19–25 kcal mol<sup>–1</sup>. Depending on the nature of substituents present on the substrate,
formation of various products has been explained. This study also
includes the heteronuclear counter part of Zeise’s dimer where
one of the Pt-metals is replaced by palladium (Pd) and nickel (Ni)
successively. The calculated activation barrier using these heteronuclear
catalysts is found to be close enough to that calculated for the catalytic
pathway using Zeise’s dimer.
2018-11-28 20:03:34
activation barrier
Zeise
heteronuclear counter part
dimer