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Reductive C-C Coupling from α,β-Unsaturated Nitriles by Intercepting Keteniminates
Lillian V A Hale1, N Marianne Sikes1, Nathaniel K Szymczak1
1Department of Chemistry, University of Michigan, 930 N. University, Ann Arbor, MI, 48109, USA.
Angewandte Chemie (International Ed. in English)
|April 25, 2019
Summary
This study introduces a new atom-economic method using hydrogen transfer catalysis to create and use nitrile anion equivalents. This approach enables efficient reductive C-C coupling reactions with α,β-unsaturated nitriles.
Area of Science:
- Organic Chemistry
- Catalysis
- Synthetic Methodology
Background:
- Hydrogen transfer catalysis offers an atom-economic approach to chemical synthesis.
- Nitrile anion equivalents are valuable synthetic intermediates.
- Developing new catalytic methods for C-C bond formation is crucial in organic synthesis.
Purpose of the Study:
- To develop an atom-economic strategy for generating and intercepting nitrile anion equivalents.
- To explore the use of hydrogen transfer catalysis with α,β-unsaturated nitriles.
- To achieve reductive C-C coupling reactions via keteniminate intermediates.
Main Methods:
- Utilizing a pincer-based Ruthenium-hydride (Ru-H) complex for catalytic hydride transfer.
- Employing α,β-unsaturated nitriles as substrates.
- Performing in situ generation of keteniminate intermediates under catalytic hydrogenation conditions.
- Electrophilic trapping of keteniminates with anhydrides.
Main Results:
- Selective 1,4-hydride transfer to α,β-unsaturated nitriles, forming structurally characterized κ-N-coordinated keteniminates.
- Successful in situ generation and electrophilic addition to keteniminates.
- High yields of α-cyanoacetates obtained through reductive C-C coupling.
Conclusions:
- This work establishes a novel application of hydrogen transfer catalysis for α,β-unsaturated nitriles.
- The developed strategy provides an efficient route to α-cyanoacetates via keteniminate intermediates.
- The methodology represents a significant advancement in catalytic reductive C-C coupling reactions.
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