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Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks (MOFs)
Published on: January 17, 2020
Recent progress in asymmetric bifunctional catalysis using multimetallic systems
Masakatsu Shibasaki1, Motomu Kanai, Shigeki Matsunaga
1Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Hongo 7-3-1, Tokyo 113-0033, Japan. mshibasa@mol.f.u-tokyo.ac.jp
Accounts of Chemical Research
|May 14, 2009
Summary
Bifunctional catalysis enables simultaneous activation of reaction partners, leading to efficient asymmetric catalysts. These catalysts are crucial for producing enantiomerically enriched compounds in organic synthesis, with applications in drug development.
Area of Science:
- Organic Chemistry
- Catalysis
- Asymmetric Synthesis
Background:
- Asymmetric catalysis is vital for producing enantiomerically enriched compounds.
- Bifunctional catalysis offers a powerful strategy for designing efficient asymmetric catalysts.
- Conventional catalysts often require harsh conditions and exhibit limited substrate scope.
Purpose of the Study:
- To review recent advances in enantioselective catalysis using bifunctional catalysts.
- To highlight the development of novel multimetallic catalysts based on bifunctional concepts.
- To showcase the application of these catalysts in synthesizing complex molecules and drug candidates.
Main Methods:
- Development of heterobimetallic rare earth-alkali metal-BINOL (REMB) complexes.
- Design of multidentate ligands such as Schiff bases and sugar-based ligands (GluCAPO, FujiCAPO).
- Investigation of amide-based ligands with rare earth metals for flexible catalytic systems.
Main Results:
- REMB complexes show efficacy in asymmetric epoxidation and cyclopropanation.
- Schiff base ligands facilitate syn-selective nitro-Mannich, anti-selective nitroaldol, and Mannich-type reactions.
- Polymetallic catalysts with sugar-based ligands are effective in asymmetric Strecker reactions.
- Amide-based systems enable asymmetric amination and Mannich-type reactions with cooperative hydrogen bonding.
- Generation of stereogenic tetrasubstituted and quaternary carbons, with applications in synthesizing therapeutics like Tamiflu.
Conclusions:
- Bifunctional catalysts offer enhanced activity, selectivity, and milder reaction conditions compared to conventional catalysts.
- The rational design of multimetallic and flexible catalytic systems is key to achieving high stereodifferentiation.
- These advanced catalytic systems hold significant promise for practical applications in asymmetric synthesis and drug discovery.
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