A Bio-Based Chiroptical Overcrowded Alkene From Flavanone: Photoreactivity and Theoretical Investigation.

Area of Science:

• Organic Chemistry
• Materials Science
• Supramolecular Chemistry

Background:

• Designing light-driven molecular machines often requires complex synthetic routes.
• Overcrowded alkenes are key components in photoresponsive materials but their synthesis can be challenging.
• Sustainable and bio-based starting materials are increasingly sought after in materials chemistry.

Purpose of the Study:

• To develop a sustainable synthesis of photoresponsive overcrowded alkenes and O-heterocyclic phenanthrene derivatives.
• To utilize a bio-based enantiopure flavanone, (-)-isolonchocarpin, as a starting material.
• To investigate the role of inherent chirality in directing molecular motion.

Main Methods:

• McMurry deoxygenative homocoupling reaction for alkene synthesis.
• Photochemical (E/Z)-isomerization and oxidative 6π-electrocyclization.
• Spin-flip time-dependent density functional theory (SF-TDDFT) for computational analysis.

Main Results:

• Successful synthesis of a sterically hindered overcrowded alkene from (-)-isolonchocarpin.
• Generation of an O-heterocyclic phenanthrene derivative with emission properties.
• Computational studies confirmed chirality-induced asymmetry in the rotational pathway.

Conclusions:

• A sustainable and efficient route to bio-based photoresponsive materials is established.
• The study demonstrates the potential of natural products in creating functional molecular machines.
• Understanding chirality-driven motion in dynamic systems is advanced.