Formal Pericyclic-Coupled Electron Transfer: I. Stepwise Formal Diels-Alder Cycloaddition Enabled by Addition-Coupled Electron Transfer

17 February 2022, Version 2
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

The formal Diels-Alder (D-A) reaction of alkenes with 1,2-diimine and related substrates is designed and studied by density functional theory (DFT), multi-reference and quasi-classical trajectory calculations in the presence of a benzoquinone-based organic oxidant. The reaction is found to occur through an Addition-Coupled Electron Transfer (ACET) with one electron transferred to the oxidant in one elementary step, affording a carbon-radical, followed by an intramolecular radical addition. The overall barrier is significantly reduced as compared to the traditional concerted D-A reaction. No concerted Pericyclic-Coupled Electron Transfer (cPeriCET), the reaction with two new bond formation events in one elementary step coupled with electron transfer, was found.

Keywords

ACET
pericyclic
single electron transfer
mechanism
DFT
quasiclassical molecular dynamics

Supplementary materials

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Description
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Supporting Information
Description
Supplemantary figures (PES for related systems), energetics and cartesian coordinates, and configuration information of the quasi-classical MD.
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