Synthesis of Parent Peropyrene and Its Derivatization

Area of Science:

• Organic Chemistry
• Materials Science

Background:

• Peropyrene (dibenzo[cd,lm]perylene) is a polycyclic aromatic hydrocarbon with potential applications in optoelectronics.
• Efficient synthesis and functionalization of peropyrene are crucial for developing advanced materials.

Purpose of the Study:

• To establish a practical and scalable synthesis of peropyrene.
• To develop regioselective methods for functionalizing peropyrene derivatives.
• To explore the utility of functionalized peropyrenes in synthesizing new materials.

Main Methods:

• Scalable synthesis of peropyrene via reductive coupling and oxidative photocyclization.
• Regioselective borylation of tetrahydro- and octahydroperopyrene using iridium catalysis.
• Synthesis of various peropyrene derivatives, including diaryl, dimeric, and macrocyclic structures.

Main Results:

• A scalable (>1 g) synthesis of peropyrene was achieved from 2,3-dihydro-1H-phenalen-1-one.
• Direct borylation of peropyrene lacked regioselectivity, yielding mixtures of borylated products.
• Tetrahydro- and octahydroperopyrene enabled regioselective borylation, yielding 2,9-diborylated and 2-(mono)borylated peropyrene, respectively.
• These borylated intermediates were used to synthesize diverse peropyrene derivatives.

Conclusions:

• A practical and scalable synthetic route to peropyrene has been established.
• Regioselective borylation of hydrogenated peropyrenes offers a viable strategy for controlled functionalization.
• Borylated peropyrenes are valuable intermediates for constructing novel peropyrene-based optoelectronic materials.