Orchestrating Multiple Aryl Rearrangements: Deciphering the Dynamics of Competitive Shifts and Shuttles on Four...

Area of Science:

• Organic Chemistry
• Synthetic Chemistry

Background:

• Multiple aryl rearrangement and translocation reactions on aromatic scaffolds are limited.
• Developing new methods for aryl migration is crucial for organic synthesis.

Purpose of the Study:

• To investigate multiple sequential 1,2-naphthyl shift and aryl shuttle reactions on heteroaromatic scaffolds.
• To understand the competition and sequential progression between 1,2-aryl shift and aryl shuttle events.
• To achieve precise control over multiple aryl migrations on a thiophene core.

Main Methods:

• Investigated sequential 1,2-naphthyl shift and aryl shuttle reactions.
• Performed mechanistic studies to elucidate reaction pathways.
• Utilized strategic orchestration of rearrangements for controlled aryl migrations.

Main Results:

• Demonstrated unprecedented aryl shuttle on a bicyclic arene.
• Delineated the competition between 1,2-aryl shift and aryl shuttle on heteroarenes.
• Achieved up to 16 sequential aryl migrations on a thiophene core.
• Established that aryl shuttle reactions proceed via a stepwise pathway.

Conclusions:

• Pioneered a new paradigm for engineering multiple molecular rearrangements on aromatic systems.
• Provided fundamental understanding of acid-mediated transformations.
• Opened avenues for programmable molecular choreography in organic synthesis and materials design.