Iron‐Catalyzed Highly Enantioselective cis ‐Dihydroxylation of Trisubstituted Alkenes with Aqueous H 2 O 2
| Autor: | Chun-Wai Tse, Liangliang Wu, Xiting Zhang, Hai-Xu Wang, Cong-Ying Zhou, Jie-Sheng Huang, Jinhu Wei, Chi-Ming Che |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
chemistry.chemical_classification
Aqueous solution 010405 organic chemistry Alkene Ligand Iron catalyzed Enantioselective synthesis Homogeneous catalysis General Chemistry Reaction intermediate General Medicine 010402 general chemistry 01 natural sciences Medicinal chemistry Catalysis 0104 chemical sciences Hydroxylation chemistry.chemical_compound chemistry Dihydroxylation Organic chemistry |
| Zdroj: | Angewandte Chemie. |
| ISSN: | 1521-3757 0044-8249 |
| DOI: | 10.1002/ange.202002866 |
| Popis: | Reliable methods for enantioselective cis-dihydroxylation of trisubstituted alkenes are scarce. The iron(II) complex cis-α-[FeII (2-Me2 -BQPN)(OTf)2 ], which bears a tetradentate N4 ligand (Me2 -BQPN=(R,R)-N,N'-dimethyl-N,N'-bis(2-methylquinolin-8-yl)-1,2-diphenylethane-1,2-diamine), was prepared and characterized. With this complex as the catalyst, a broad range of trisubstituted electron-deficient alkenes were efficiently oxidized to chiral cis-diols in yields of up to 98 % and up to 99.9 % ee when using hydrogen peroxide (H2 O2 ) as oxidant under mild conditions. Experimental studies (including 18 O-labeling, ESI-MS, NMR, EPR, and UV/Vis analyses) and DFT calculations were performed to gain mechanistic insight, which suggested possible involvement of a chiral cis-FeV (O)2 reaction intermediate as an active oxidant. This cis-[FeII (chiral N4 ligand)]2+ /H2 O2 method could be a viable green alternative/complement to the existing OsO4 -based methods for asymmetric alkene dihydroxylation reactions. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
Plný text