Base-Promoted Electrochemical CoII-catalyzed Enantioselective C−H Oxygenation
Gang Zhou
Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027 China
Search for more papers by this authorJia-Hao Chen
Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027 China
Search for more papers by this authorQi-Jun Yao
Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027 China
Search for more papers by this authorFan-Rui Huang
Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027 China
Search for more papers by this authorZhen-Kai Wang
Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027 China
Search for more papers by this authorCorresponding Author
Bing-feng Shi
Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027 China
Search for more papers by this authorGang Zhou
Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027 China
Search for more papers by this authorJia-Hao Chen
Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027 China
Search for more papers by this authorQi-Jun Yao
Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027 China
Search for more papers by this authorFan-Rui Huang
Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027 China
Search for more papers by this authorZhen-Kai Wang
Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027 China
Search for more papers by this authorCorresponding Author
Bing-feng Shi
Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310027 China
Search for more papers by this authorGraphical Abstract
The first electrochemical CoII-catalyzed enantioselective C−H alkoxylation is reported. A broad range of alkoxylated phosphinamides were obtained in good yields with excellent enantioselectivities (up to 98 % yield and >99 % ee). A cobalt(III) alcohol complex was prepared and characterized, and was found to be a key intermediate in this reaction. Mechanistic studies revealed that the oxidation of CoIII to CoIV was facilitated by a base.
Abstract
Metalla-electrocatalyzed C−H oxygenation represents one of the most straightforward and sustainable approaches to access valuable oxygenated molecules. Despite the significant advances, the development of enantioselective electrochemical C−H oxygenation reaction is very challenging and remains elusive. Herein, we described the first electrochemical CoII-catalyzed enantioselective C−H alkoxylation. A broad range of enantioenriched alkoxylated phosphinamides were obtained in good yields with excellent enantioselectivities (up to 98 % yield and >99 % ee). An unusual cobalt(III) alcohol complex was prepared and fully characterized, which was proven to be a key intermediate of this C−H alkoxylation reaction. Mechanistic studies revealed that the oxidation of CoIII to CoIV was facilitated by a base and the whole process proceeded through a cobalt(III/IV/II) catalytic cycle.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the Supporting Information of this article.
Supporting Information
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| Filename | Description |
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| anie202302964-sup-0001-3ai.cif787.7 KB | Supporting Information |
| anie202302964-sup-0001-3ai_checkcif.pdf85.8 KB | Supporting Information |
| anie202302964-sup-0001-3al.cif851.2 KB | Supporting Information |
| anie202302964-sup-0001-3al_cifreport.pdf124.8 KB | Supporting Information |
| anie202302964-sup-0001-misc_information.pdf11 MB | Supporting Information |
| anie202302964-sup-0001-[CoIII][MeOH].cif1.2 MB | Supporting Information |
| anie202302964-sup-0001-[CoIII][MeOH]_checkcif.pdf94.6 KB | Supporting Information |
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