Hidden intermediate activation: a concept to elucidate the reaction mechanism of the Schmittel cyclization of enyne

Hidden intermediate activation: a concept to elucidate the reaction mechanism of the Schmittel cyclization of enyne–allenes

Published:2023 Issue:8 Volume:25 Page:6050-6059
ISSN:1463-9076
Container-title:Physical Chemistry Chemical Physics
language:en
Short-container-title:Phys. Chem. Chem. Phys.

Author:

Durán Rocío¹²^ORCID,Barrales-Martínez César³⁴^ORCID,Matute Ricardo A.⁴⁵^ORCID

Affiliation:

1. Centro de Bioinformática, Simulación y Modelado (CBSM), Facultad de Ingeniería, Universidad de Talca, Campus Lircay, Talca 3460000, Chile

2. Instituto de Investigación Interdisciplinaria (I3), Universidad de Talca, Campus Lircay, Talca 3460000, Chile

3. Departamento de Química Orgánica y Fisicoquímica, Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Sergio Livingstone 1007, Independencia, Santiago 8380492, Chile

4. Centro Integrativo de Biología y Química Aplicada (CIBQA), Universidad Bernardo O’Higgins, General Gana 1702, Santiago 8370854, Chile

5. Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA

Abstract

The Diabatic Model of Intermediate Stabilization (DMIS) provides critical elements to analyze the transit from a one-step to a stepwise mechanism of the Schmittel cyclization by stabilizing a full hidden intermediate.

Funder

Fondo Nacional de Desarrollo Científico y Tecnológico

Comisión Nacional de Investigación Científica y Tecnológica

Publisher

Royal Society of Chemistry (RSC)

Subject

Physical and Theoretical Chemistry,General Physics and Astronomy

Link

http://pubs.rsc.org/en/content/articlepdf/2023/CP/D2CP04684A

Reference64 articles.

1. Switching from the Myers Reaction to a New Thermal Cyclization Mode in Enyne-Allenes

2. Steric effects in enyne-allene thermolyses: Switch from the Myers-Saito reaction to the C2C6-cyclization and DNA strand cleavage