Synlett 2022; 33(09): 890-892
DOI: 10.1055/a-1799-7517
cluster
Mechanochemistry

Stereoelectronic Effects in Force-Accelerated Retro-Diels–Alder Reactions

Lik Chun Wu
,
G.D.B. is a Royal Society University Research Fellow.


Abstract

In polymer mechanochemistry, mechanosensitive molecules (mechanophores) are activated upon elongation of anchored polymer arms. The reactivity of a mechanophore can be influenced by a variety of structural factors, including the geometry of attachment of the polymer arms and the nature of eventual substituents. Here we investigate stereoelectronic effects in force-accelerated Diels–Alder reactions using the CoGEF (Constrained Geometries simulate External Force) calculation method. We found that the presence of an electron-donating heteroatom on the diene leads to a lower activation force, and that the mechanochemical reactivity is suppressed when the anchor group is attached to a central rather than lateral position.

Supporting Information



Publication History

Received: 05 February 2022

Accepted after revision: 15 March 2022

Accepted Manuscript online:
15 March 2022

Article published online:
06 May 2022

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