Dual Co/Photoredox-Catalyzed Regio- and Stereoselective Allyl Homocoupling Providing Functionalized 1,5-Dienes

Area of Science:

• Organic Chemistry
• Catalysis
• Synthetic Methodology

Background:

• Vinyl cyclic carbonates are versatile building blocks in organic synthesis.
• Allyl precursors are crucial for constructing complex carbon skeletons.
• Quaternary centers present synthetic challenges in stereoselective transformations.

Purpose of the Study:

• To develop a novel catalytic method for synthesizing functionalized 1,5-dienes.
• To achieve exclusive regio- and stereocontrol in a formal homocoupling reaction.
• To explore the utility of the synthesized dienes through product diversification.

Main Methods:

• Dual catalysis employing cobalt complexes and organophotoredox catalysts.
• Utilizing vinyl cyclic carbonates as allyl precursors.
• Employing a bulky N^P^N ligand for stereochemical control.

Main Results:

• Successful generation of functionalized 1,5-dienes featuring a quaternary center.
• Exclusive regio- and stereocontrol achieved through the use of a bulky N^P^N ligand.
• Demonstrated site-selective transformations on the synthesized products, showcasing their synthetic utility.

Conclusions:

• The developed dual catalytic system provides an efficient route to complex dienes.
• The bulky N^P^N ligand is critical for achieving high levels of stereoselectivity.
• The synthesized dienes are valuable intermediates for further synthetic elaborations.