TS1 (cis-TSIC). Torquoselectivity Unusual Ring-Opening Electrocyclic Reactions.

Описание: Intrinsic Reaction Coordinate calculated by means the
software Gaussian 16, the B3LYP/6-311G(d,p)
method/basis-set have been used for the calculation.

REFERENCE:

TITLE:
Study of the Torquoselectivity of a Set of Unusual
Ring-Opening Electrocyclic Reactions: Determination of the
Electronic Bonding Structure Through the Methodologies of
Natural Bond Orbital Analysis and Quantum Theory of
Atoms in Molecules, and Analysis of the Electronic Reaction
Mechanism Through Bond Reactivity Descriptors.

Authors:

Jesús Sánchez-Márquez | Alejandro Morales-Bayuelo

International Journal of Quantum Chemistry, 2024; 124:e27494

https://doi.org/10.1002/qua.27494

ABSTRACT:

In this work, we have studied the torquoselectivity of a set of
unusual ring-opening electrocyclic reactions that have not been
successfully rationalized using models based on orbital symmetry
nor have they been explained by steric hindrance. Firstly, the
corresponding transition states have been obtained, and it has
been verified that the intrinsic reaction coordinates associated with
these transition states are consistent with the reactants and
products of the reactions studied. This has allowed us to theoretically
calculate the reaction barriers (with their corresponding thermal
corrections) and compare them with the corresponding experimental
values. In a second step, we have analyzed the electronic bonding
structure using the methodologies of Natural Bond
Orbital Analysis and Quantum Theory of Atoms in Molecules,
searching for interactions that may significantly stabilize the transition
states. Finally, we have analyzed the reactivity using a recent
model that has allowed us to calculate the corresponding bond
reactivity descriptors.