Utilizing Vinylcyclopropane Reactivity: Palladium-Catalyzed Asymmetric [5+2] Dipolar Cycloadditions
Miao-Miao Li1, Qin Xiong2, Bao-Le Qu1
1CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei, 430079, China.
This study introduces a new palladium-catalyzed reaction using vinylcyclopropanes (VCPs) and α-diazoketones to create enantioenriched seven-membered lactones. This visible-light-driven method offers high efficiency and selectivity in modern synthetic chemistry.
Area of Science:
- Organic Chemistry
- Catalysis
- Synthetic Chemistry
Background:
- Vinylcyclopropanes (VCPs) are versatile building blocks in transition-metal-catalyzed reactions.
- Developing novel synthetic methodologies for constructing complex cyclic architectures is crucial in modern chemistry.
Purpose of the Study:
- To develop a palladium-catalyzed, visible-light-driven asymmetric [5+2] cycloaddition reaction.
- To utilize vinylcyclopropanes (VCPs) and α-diazoketones for the synthesis of enantioenriched seven-membered lactones.
Main Methods:
- Employing a palladium catalyst and visible light irradiation.
- Switching the reactivity of a palladium-containing dipolar intermediate.
- Utilizing vinylcyclopropanes (VCPs) and α-diazoketones as substrates.
Main Results:
- Successful synthesis of enantioenriched seven-membered lactones with good yields (52-92%).
- Achieved high enantioselectivities (up to 99:1 er) and diastereoselectivities (up to 12.5:1 dr).
- Demonstrated the reaction's applicability with 23 examples.
Conclusions:
- The developed method provides an efficient route to valuable seven-membered lactones.
- The strategy of switching dipolar intermediate reactivity expands synthetic possibilities.
- Computational studies support the observed selectivity, offering mechanistic insights.
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