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Palladium(II)-Catalyzed Enantioselective Reactions Using COP Catalysts
Jeffrey S Cannon1, Larry E Overman1
1Department of Chemistry, University of California , 1102 Natural Sciences II, Irvine, California 92697-2025, United States.
Chiral cobalt oxazoline palladacyclic (COP) catalysts enable enantioselective synthesis of allylic compounds via palladium(II) catalysis. These catalysts facilitate key reactions like rearrangements and substitutions, providing valuable chiral building blocks.
Area of Science:
- Organic Chemistry
- Asymmetric Catalysis
- Palladium Catalysis
Background:
- Allylic amides, amines, and esters are crucial synthetic intermediates.
- Enantioselective synthesis of these compounds under mild conditions remains a challenge.
- Palladium(II) catalysis offers a route through functionalization of prochiral double bonds.
Purpose of the Study:
- To develop and utilize enantiopure palladium(II) catalysts of the COP family.
- To synthesize enantioenriched allylic compounds from prochiral allylic alcohols.
- To investigate the mechanism of enantioselective COP-catalyzed reactions.
Main Methods:
- Development of chiral cobalt oxazoline palladacyclic (COP) palladium(II) catalysts.
- Application of COP catalysts in [3,3]-sigmatropic rearrangements of allylic imidates.
- Utilizing COP catalysts in SN2' reactions for allylic substitution.
Main Results:
- COP catalysts enable enantioselective rearrangement of allylic imidates to allylic trichloroacetamides.
- Acetate-bridged COP dimer ([COP-OAc]2) catalyzes SN2' reactions yielding branched allylic esters and ethers with high enantioselectivity.
- Nucleopalladation is identified as the enantiodetermining step in COP-catalyzed reactions.
Conclusions:
- COP catalysts are highly effective for the enantioselective synthesis of valuable allylic building blocks.
- The cyclobutadienyl 'floor' of COP catalysts is critical for transmitting chiral information.
- COP catalysts have broad applications in synthesizing biologically active chiral molecules.
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