Point-to-Point Ultra-Remote Asymmetric Control with Flexible Linker

Area of Science:

• Organic Chemistry
• Supramolecular Chemistry
• Catalysis

Background:

• Asymmetric autocatalysis is crucial for synthesizing chiral molecules.
• Achieving long-range stereochemical control in catalytic systems remains a significant challenge.
• Supramolecular interactions offer a potential strategy for organizing catalytic and substrate components.

Purpose of the Study:

• To demonstrate ultra-remote intramolecular asymmetric control over 38 bonds.
• To achieve highly stereoselective induction via direct supramolecular orientation.
• To explore the application of designed molecules in asymmetric autocatalysis.

Main Methods:

• Design of molecules with pyrimidine moieties at terminal positions of a flexible methylene chain.
• Utilizing direct supramolecular orientation to align catalytic and reactive sites.
• Investigating the stereoselectivity of the diisopropylzinc addition reaction.

Main Results:

• Successful implementation of an ultra-remote 1,39-asymmetric induction over 38 bonds.
• Demonstration of highly stereoselective diisopropylzinc addition.
• Validation of the direct supramolecular orientation principle for remote asymmetric control.

Conclusions:

• Direct supramolecular orientation is an effective strategy for achieving ultra-remote asymmetric control.
• Designed molecular architectures can facilitate long-range stereochemical induction in catalysis.
• This methodology opens new avenues for the synthesis of complex chiral molecules.