Citation: Yuhan Liu, Jingyang Zhang, Gongming Yang, Jian Wang. Highly enantioselective carbene-catalyzed δ-lactonization via radical relay cross-coupling[J]. Chinese Chemical Letters, ;2025, 36(1): 109790. doi: 10.1016/j.cclet.2024.109790 shu

Highly enantioselective carbene-catalyzed δ-lactonization via radical relay cross-coupling

School of Pharmaceutical Sciences, Key Laboratory of Bioorganic Phosphorous Chemistry and Chemical Biology (Ministry of Education), Tsinghua University, Beijing 100084, China

wangjian2012@tsinghua.edu.cn

Received Date: 20 December 2023
Revised Date: 9 March 2024
Accepted Date: 18 March 2024
Available Online: 20 March 2024

Figures(6)

An N-heterocyclic carbene (NHC) catalyzed enantioselective cyclisation and trifluoromethylation of olefins with cinnamaldehydes via radical relay cross-coupling in the presence of Togni reagent is reported and δ-lactones tolerated with stereogenic centers at β- and γ-positions are obtained in moderate to high yields and with high enantioselectivities. Further computational studies explain that the radical cross-coupling step is the key to determining the enantioselectivity. Energy analysis of key transition states and intermediates also provides a reasonable explanation for the difficulty of diastereoselective control. DFT calculations also reveal that the hydrogen-bonding interaction plays a vital role in the promotion of this chemistry.
- Carbene organocatalysis,
- Radical relay cross-coupling,
- Trifluoromethylation,
- Cyclisation,
- δ-Lactone
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