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Published on: May 26, 2019
1,5-Conjugate Addition: A Potentially Valuable Synthetic Tool
Jing-Ming Zhang1,2, Shi-Feng Tao1,2, Xing-Kai Zhao1,2
1School of Chemistry and Materials Science, Hangzhou Institute For Advanced Study, University of Chinese Academy of Sciences, Hangzhou, China.
Umpolung 1,5-conjugate addition, rarely explored due to electronic mismatch, is now feasible using palladium hydride catalysis. This breakthrough enables enantioselective introduction of nucleophiles and synthesis of cyclic structures, establishing a new synthetic model.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
Background:
- 1,4- and 1,6-conjugate addition reactions are well-established.
- Umpolung 1,5-addition is electronically mismatched and underexplored.
Purpose of the Study:
- To explore the feasibility and applications of umpolung 1,5-addition reactions.
- To establish 1,5-conjugate addition as a new synthetic model.
Main Methods:
- Utilizing palladium hydride catalysis.
- Employing electron-deficient conjugated dienes.
- Introducing diverse C-, O-, and N-based nucleophiles.
Main Results:
- Demonstrated the feasibility of umpolung 1,5-addition.
- Achieved enantioselective nucleophilic introduction to the γ-position.
- Synthesized privileged cyclic structures via cascade processes with high stereocontrol.
Conclusions:
- Umpolung 1,5-conjugate addition is a viable and versatile synthetic strategy.
- This reaction expands the scope of conjugate addition chemistry.
- 1,5-conjugate addition is emerging as a powerful new synthetic model.
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