Highly Enantioselective Regiodivergent and Catalytic Parallel Kinetic Resolution

Area of Science:

• Organometallic Chemistry
• Asymmetric Catalysis
• Stereoselective Synthesis

Background:

• Chiral recognition is crucial for controlling enantioselectivity in chemical reactions.
• Developing catalytic methods for enantioselective and regiodivergent transformations remains a significant challenge in organic synthesis.

Purpose of the Study:

• To achieve the first organometallic catalytic kinetic resolution with enantio- and regiodivergent reactivity.
• To explore the use of chiral copper complexes with phosphoramidite ligands for asymmetric synthesis.

Main Methods:

• Utilized chiral copper complexes derived from a non-racemic phosphoramidite ligand (L*).
• Employed semirigid vinyloxiranes with blocked s-cis or s-trans conformations as substrates.
• Performed a two-step catalytic kinetic resolution process.

Main Results:

• Demonstrated an unusual regiodivergent catalytic kinetic resolution in a C-C bond-forming organometallic reaction.
• Achieved highly effective discrimination of vinyloxirane enantiomers by the chiral copper catalyst.
• Obtained separable regioisomeric products with very high stereocontrol.

Conclusions:

• The developed method represents a novel approach to enantio- and regiodivergent reactivity in organometallic catalysis.
• Chiral copper-phosphoramidite complexes are effective in controlling both enantioselectivity and regioselectivity in the kinetic resolution of vinyloxiranes.