A unique Pd-catalysed Heck arylation as a remote trigger for cyclopropane selective ring-opening.

Area of Science:

• Organic Synthesis
• Catalysis
• Stereochemistry

Background:

• Creating complex acyclic molecules with multiple stereocenters, especially quaternary carbons, is a significant challenge in organic synthesis.
• Developing methods for regioselective functionalization distant from reactive sites is crucial for efficient molecular construction.

Purpose of the Study:

• To develop a novel synthetic strategy for constructing complex acyclic scaffolds.
• To demonstrate the utility of palladium-catalyzed Heck arylation as a trigger for cyclopropane ring-opening and subsequent chain-walking.
• To achieve stereoselective synthesis of acyclic compounds containing multiple stereogenic centers.

Main Methods:

• Utilizing regioselective Heck arylation of terminal olefins to initiate cyclopropane ring-opening.
• Employing palladium catalysis to drive a chain-walking process.
• Using stereodefined polysubstituted cyclopropane precursors.

Main Results:

• The developed method successfully achieved regioselective Heck arylation triggering cyclopropane ring-opening.
• The reaction demonstrated efficiency and versatility, proceeding irrespective of the distance between the double bond and alcohol sites.
• Stereodefined acyclic scaffolds with multiple stereocenters, including a quaternary carbon, were synthesized in good yields.

Conclusions:

• Merging catalytic chain walking with selective C-C bond cleavage offers a powerful approach for constructing linear skeletons with multiple stereocenters.
• This methodology provides a versatile route to complex stereoenriched acyclic molecules.