Chemodivergent Accesses to Hetero-Bicyclo[3.3.1]nonenes

Area of Science:

• Organic Chemistry
• Catalysis
• Synthetic Methodology

Background:

• Achmatowicz rearrangement products (ARPs) are versatile intermediates.
• Developing efficient methods for constructing complex molecular scaffolds is crucial in organic synthesis.
• Chemodivergent reactions offer pathways to diverse molecular architectures.

Purpose of the Study:

• To develop practical and efficient methods for synthesizing highly functionalized bicyclic scaffolds.
• To explore sterically controlled and rare-earth-catalyzed chemodivergent annulations.
• To enable the synthesis of enantiopure bicyclic compounds.

Main Methods:

• Utilizing (3 + 3) annulation reactions between enamines and ARPs.
• Employing sterically controlled conditions.
• Leveraging rare-earth metal catalysis.
• Starting with enantiopure ARPs for enantioselective synthesis.

Main Results:

• Efficient construction of two distinct bicyclic scaffolds: 7-oxa-2-azabicyclo[3.3.1]non-3-enes and 3-oxabicyclo[3.3.1]non-6-enes.
• Synthesis of highly functionalized, three-dimensional, and rigid molecular structures.
• Successful preparation of enantiopure products from enantiopure ARPs.

Conclusions:

• The developed methods provide practical access to valuable bicyclic scaffolds.
• Rare-earth catalysis enables efficient chemodivergent annulations.
• The methodology is applicable for synthesizing enantiopure complex molecules.