Impact of the Olefin and Diazene Structure on the Heterofunctional Azo Metathesis Catalyzed by the First-Generation Grubbs Catalyst

In this work, we computationally studied the influence of the change in the substrate structure on the course of the heterofunctional cross-metathesis reaction between azo compounds and olefins catalyzed by the first-generation Grubbs catalyst. The highest reaction rates were predicted for symmetric...

Full description

Saved in:
Bibliographic Details
Published in:Organometallics 2024-09, Vol.43 (18), p.2044-2051
Main Authors: Jawiczuk, Magdalena, Trzaskowski, Bartosz
Format: Article
Language:English
Citations: Items that this one cites
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:In this work, we computationally studied the influence of the change in the substrate structure on the course of the heterofunctional cross-metathesis reaction between azo compounds and olefins catalyzed by the first-generation Grubbs catalyst. The highest reaction rates were predicted for symmetric, bulky diazenes and sterically uncrowded olefins. Other studied azo compounds have much higher energy barriers in the crucial steps in the catalyst initiation phase, while larger olefins are characterized by high energy barriers in the second part of the catalytic cycle. Our analysis suggests that Grubbs-like catalysts can be efficiently used in heterofunctional azo metathesis only for a limited number of olefin-azo compound combinations, such as 1,2-diphenyldiazene and ethylene to produce N-phenylmethanimine.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.4c00264