Reductive Decarboxylative Alkynylation of N-Hydroxyphthalimide Esters with Bromoalkynes
Liangbin Huang1, Astrid M Olivares1, Daniel J Weix1
1Department of Chemistry, University of Rochester, Rochester, New York, 14627-0216, USA.
A novel nickel-catalyzed reaction enables the synthesis of alkynes using N-hydroxyphthalimide esters and bromoalkynes. This efficient method avoids harsh conditions and offers broad functional group tolerance for diverse applications.
Area of Science:
- Organic Chemistry
- Catalysis
- Synthetic Methodology
Background:
- Traditional alkyne synthesis methods can be limited in scope or require harsh conditions.
- Developing new catalytic systems for carbon-carbon bond formation is crucial for organic synthesis.
Purpose of the Study:
- To present a new nickel-catalyzed decarboxylative coupling method for synthesizing terminal and internal alkynes.
- To explore the use of N-hydroxyphthalimide esters as coupling partners in reductive cross-electrophile coupling reactions.
Main Methods:
- Nickel-catalyzed decarboxylative coupling of N-hydroxyphthalimide esters with bromoalkynes.
- Utilizing a C(sp)-X electrophile in a reductive cross-electrophile coupling reaction.
- Investigating the reaction mechanism through mechanistic studies.
Main Results:
- The reaction successfully synthesized internal alkynes in 41-95% yields.
- The method does not require a photocatalyst, light, or strong oxidant.
- A broad scope of carboxylic acid and alkyne coupling partners was demonstrated, with tolerance for various functional groups.
Conclusions:
- This study introduces a versatile and efficient method for alkyne synthesis.
- The reaction proceeds via a nickel-mediated pathway, likely involving an alkynylnickel intermediate.
- The developed methodology offers a valuable tool for constructing complex organic molecules.
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