Long-range isomerisation/cyclopropane isomerisation/cycloisomerisation/aromatisation reactions using multifunctional...

Area of Science:

• Organic Chemistry
• Catalysis
• Synthetic Methodology

Background:

• Transition-metal-catalyzed chain-walking reactions are key for remote alkene functionalization.
• Integrating chain-walking with C-C bond activation is an underexplored area in catalysis.

Purpose of the Study:

• To develop a rhodium-catalyzed system combining long-range alkyl chain-walking and cyclopropyl C-C bond cleavage.
• To achieve efficient synthesis of substituted benzofurans via a novel cooperative catalytic strategy.

Main Methods:

• Rhodium-catalyzed reaction development.
• Exploration of migratory alkene isomerization and cyclopropane activation.
• Mechanistic studies using temperature-controlled and time-resolved NMR.

Main Results:

• Successful combination of long-range chain-walking with selective cyclopropyl C-C bond cleavage in one catalytic system.
• Efficient formation of substituted benzofurans under mild conditions.
• Demonstration of catalyst migration enabling spatially separated C-C bond activation.

Conclusions:

• The developed cooperative catalytic strategy orchestrates spatially separated reaction events.
• This work expands the scope of chain-walking catalysis by integrating it with C-C bond activation.
• The findings pave the way for new synthetic routes in organic chemistry.