Inter- and intramolecular-bridge-mediated electron transfer in aliphatic halides

Area of Science:

• Organic Chemistry
• Computational Chemistry

Background:

• Anionic surfaces of chlorinated polycyclic ketones are key intermediates in organic reactions.
• Understanding their behavior is crucial for predicting reaction outcomes.

Purpose of the Study:

• To investigate the anionic surfaces of various chlorinated bicyclic, adamantane, and tricyclic ketones.
• To elucidate the factors controlling their reductive cleavage mechanisms.

Main Methods:

• Density Functional Theory (DFT) calculations were employed.
• Full geometry optimization was performed in solution for all studied compounds.

Main Results:

• The reductive cleavage is governed by polycyclic rigidity, radical formation stability, and carbonyl/C-Cl positioning.
• Two mechanisms were identified: concerted-dissociative and stepwise via radical anions.
• 5-Chloroadamantan-2-one was identified as optimal for the stepwise mechanism.

Conclusions:

• Molecular structure significantly influences the reductive cleavage pathways of chlorinated polycyclic ketones.
• The findings provide insights into controlling reaction mechanisms through substrate design.