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Pd-catalyzed enantioselective allyl-allyl cross-coupling
Ping Zhang1, Laura A Brozek, James P Morken
1Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
This study details a palladium-catalyzed cross-coupling reaction between allylic carbonates and allylboronates. Ligand bite angle controls regioselectivity, favoring branched products, and chiral ligands enable enantioselective synthesis of allylic substitution products.
Area of Science:
- Organic Chemistry
- Catalysis
- Synthetic Methodology
Background:
- Palladium-catalyzed cross-coupling reactions are vital in organic synthesis.
- Controlling regioselectivity and enantioselectivity in allylic substitution remains a key challenge.
Purpose of the Study:
- To develop a regioselective and enantioselective Pd-catalyzed cross-coupling of allylic carbonates and allylboronates.
- To investigate the influence of ligand bite angle on reaction regioselectivity.
Main Methods:
- Utilized palladium catalysis for cross-coupling reactions.
- Employed various ligands, including small-bite-angle and chiral variants.
- Characterized reaction products to determine regioselectivity and enantioselectivity.
Main Results:
- Demonstrated that small-bite-angle ligands favor the branched allylic substitution product.
- Established a mechanistic pathway involving a 3,3' reductive elimination.
- Achieved high enantioselectivity using chiral ligands for both aromatic and aliphatic allylic carbonates.
Conclusions:
- Ligand bite angle is a critical factor in controlling regioselectivity in this Pd-catalyzed reaction.
- The developed method provides a versatile route to enantiomerically enriched allylic substitution products.
- This work expands the scope of Pd-catalyzed allylic functionalization.
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