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Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks (MOFs)
Published on: January 17, 2020
Sterically Engineered Mo─V Cluster Catalyst for Switchable Z/E-Selective Alkyne Hydrophosphorylation
Yu-Feng Liu1, Bao-Kuan Chen2, Guo-Ping Yang1
1Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation, Jiangxi Province Key Laboratory of Functional Organic Polymers, East China University of Technology, Nanchang, Jiangxi, China.
This study introduces a novel steric hindrance-mediated strategy for stereodivergent alkyne hydrophosphorylation, enabling switchable Z/E selectivity in synthesizing alkenylphosphine oxides. The method offers a tunable and efficient approach for creating valuable chemical compounds.
Area of Science:
- Synthetic Chemistry
- Organometallic Chemistry
- Catalysis
Background:
- Stereodivergent synthesis of alkenylphosphine oxides is challenging.
- Existing methods lack tunable Z/E selectivity.
Purpose of the Study:
- To develop a steric hindrance-mediated strategy for switchable Z/E selectivity in alkyne hydrophosphorylation.
- To synthesize β-(Z)- and β-(E)-alkenylphosphine oxides with high selectivity.
Main Methods:
- Utilized a sterically hindered metal-organic-functionalized phosphovanadomolybdate catalyst.
- Employed a steric repulsion mechanism for Z-selectivity.
- Incorporated silver acetate (AgOAc) as a stereochemical modulator for E-selectivity.
Main Results:
- Achieved up to 81% yield of β-(Z)-alkenylphosphine oxides with a Z/E ratio of 21:1.
- Obtained up to 80% yield of β-(E)-alkenylphosphine oxides with an E/Z ratio of 15:1.
- Demonstrated broad substrate tolerance, chemo-, and regioselectivity, including applications in complex molecule synthesis.
Conclusions:
- The developed heterogeneous catalytic system provides a practical solution for stereodivergent alkyne hydrophosphorylation.
- Offers fundamental insights into steric control in transition metal-catalyzed reactions.
- Enables efficient synthesis of valuable alkenylphosphine oxide derivatives.
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