Citation: Jun Shi, Xueting Zhou, Bing-Qing Yang, Biaobiao Jiang, Wei Wu, Hai Ren. Single-electron transfer enables enantioselective synthesis of spirooxindoles via dual copper and phosphoric acid catalysis[J]. Chinese Chemical Letters, ;2026, 37(4): 111250. doi: 10.1016/j.cclet.2025.111250 shu

Single-electron transfer enables enantioselective synthesis of spirooxindoles via dual copper and phosphoric acid catalysis

Jun Shi ^{a, b, 1} ,
Xueting Zhou ^{a, b, 1} ,
Bing-Qing Yang ^{a, b, 1} ,
Biaobiao Jiang ^{a, b, c} ,
Wei Wu ^{a, b, *,} ,
Hai Ren ^{a, b, *,}

a.
State Key Laboratory of Discovery and Utilization of Functional Components in Traditional Chinese Medicine, Guizhou Medical University, Guiyang 550014, China
b.
Natural Products Research Center of Guizhou Province, Guiyang 550014, China
c.
National Key Laboratory of Green Pesticide, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University, Guiyang 550025, China

wuwei@gmc.edu.cn

renhai@gmc.edu.cn

Received Date: 22 January 2025
Revised Date: 10 April 2025
Accepted Date: 22 April 2025
Available Online: 22 April 2025

Figures(6)

The single-electron transfer-induced oxidative transformation of indoles has been extensively explored in recent years. However, research toward high enantioselective control in this reaction is rare. Herein, we report an enantioselective catalytic single-electron transfer-induced oxidative rearrangement of cyclic indoles enabled by dual chiral copper/phosphoric acid catalysis. Using atmospheric oxygen (O₂) as the terminal oxidant, the reactions of tetrahydro-β-carbolines, tetrahydropyrano[3,4-b]indoles and the challenging tetrahydrocarbazoles are all realized, providing diverse rearrangement products including pyrrolidinyl-, tetrahydrofuranyl- and cyclopentyl-bearing spiroindolinones in good yields with high enantioselectivities. The synthetic utility of this protocol was demonstrated in a concise synthesis of (+)-coerulescine and (+)-horsfiline. These findings would provide new insights and opportunities for future asymmetric oxidative radical reaction design.
- Spirooxindole,
- Single-electron transfer,
- Rearrangement,
- Copper,
- Dual catalysis
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