Dearomative Skeletal Editing of Benzenoids via Diradical

Area of Science:

• Organic Chemistry
• Synthetic Chemistry
• Photochemistry

Background:

• Dearomative skeletal editing of benzenoids offers a pathway to valuable carbon frameworks.
• The Büchner reaction transforms benzenoids into cycloheptatrienes but faces compatibility and selectivity challenges.
• Integrating dearomative cycloaddition with skeletal editing remains underdeveloped.

Purpose of the Study:

• To develop a unified system for dearomative skeletal editing and cycloaddition of benzenoids.
• To establish an energy-transfer-induced intermolecular reaction between benzenoids and alkynes.
• To construct diverse polycyclic frameworks with high selectivity.

Main Methods:

• Utilized N-acylimines as diradical precursors.
• Employed energy-transfer-induced photochemistry.
• Integrated photoinduced skeletal editing with dearomative cycloaddition.
• Performed experimental and computational studies.

Main Results:

• Demonstrated an intermolecular dearomative skeletal editing reaction of benzenoids with diverse alkynes.
• Successfully constructed structurally diverse polycyclic frameworks.
• Achieved high chemo-, regio-, and diastereoselectivities.
• Overcame challenges in reactivity and selectivity.

Conclusions:

• The developed protocol provides unprecedented access to complex polycyclic structures.
• The merging of photoinduced skeletal editing and dearomative cycloaddition is effective.
• The study elucidates the diradical mechanism and selectivity origins.