# Noncovalent Interaction Effects on the Acyl Radical Reaction of Bicyclo[2.2.2]octanone: Selective Formation of Rearrangement and Cyclization Products

## TL;DR

This study explores how molecular structure affects the outcome of a chemical reaction involving bicyclo[2.2.2]octenone.

## Contribution

The paper introduces how noncovalent interactions guide selectivity in acyl radical reactions.

## Key findings

- Allylic substituent orientation influences the six-membered fused ring reaction.
- Steric hindrance at the alkene bridge and bridgehead affects reaction selectivity.
- Noncovalent interactions are key to determining product formation.

## Abstract

The influence of allylic substituent orientation on the
six-membered
fused ring, as well as the steric hindrance at the alkene bridge (R1 and R2) and bridgehead (R3), on the
thiol-mediated acyl radical rearrangement/cyclization of bicyclo[2.2.2]­octenone
was investigated. A combined analysis using density functional theory
calculations and interaction region indicator analysis suggests that
reaction selectivity is driven by functional group noncovalent interactions.