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Cobalt-catalyzed enantioselective intramolecular reductive cyclization via electrochemistry
Shiquan Gao1, Chen Wang2, Junfeng Yang3,4
1Department of Chemistry, Fudan University, 2005 Songhu Road, Shanghai, 200438, China.
Nature Communications
|March 9, 2023
Summary
This study introduces a novel electrochemical method for cobalt-catalyzed asymmetric cyclization of enynes. This approach efficiently produces carbocycles and heterocycles with high selectivity using water as a hydride source.
Area of Science:
- Organic Chemistry
- Electrochemistry
- Catalysis
Background:
- Transition-metal catalyzed asymmetric cyclization of 1,6-enynes is a key synthetic strategy.
- Electrochemical methods for such transformations are scarce.
- Water as a green hydride source is highly desirable.
Purpose of the Study:
- To develop a novel cobalt-catalyzed enantioselective intramolecular reductive coupling of enynes under electrochemical conditions.
- To utilize water as a sustainable hydride source.
- To expand the scope of electrocatalytic asymmetric synthesis.
Main Methods:
- Cobalt-catalyzed enantioselective intramolecular reductive coupling of 1,6-enynes.
- Electrochemical synthesis utilizing water as the hydride source.
- Density Functional Theory (DFT) studies to elucidate reaction mechanisms.
Main Results:
- Achieved good yields of carbocycles and heterocycles.
- Demonstrated high regio- and enantioselectivities in the products.
- Established a general substrate scope for the reaction.
- DFT studies indicated the preference for oxidative cyclization pathway.
Conclusions:
- This work presents a rare and efficient cobalt-catalyzed enantioselective transformation via electrochemistry.
- The developed method offers a sustainable and selective route for synthesizing complex carbocycles and heterocycles.
- The findings pave the way for further advancements in green electrocatalytic asymmetric synthesis.
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