Stereospecific and Chemoselective Copper‐Catalyzed Deaminative Silylation of Benzylic Ammonium Triflates
| Autor: | Jonas Scharfbier, Benjamin M. Gross, Martin Oestreich |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
inorganic chemicals
Reaction mechanism Silylation silanes 010402 general chemistry 01 natural sciences Medicinal chemistry Catalysis Transmetalation chemistry.chemical_compound Stereospecificity stereospecificity Nucleophilic substitution Ammonium Silanes 010405 organic chemistry Communication General Chemistry Communications 0104 chemical sciences Homogeneous Catalysis 540 Chemie und zugeordnete Wissenschaften chemistry transmetalation copper ddc:540 nucleophilic substitution |
| Zdroj: | Angewandte Chemie (International Ed. in English) |
| ISSN: | 1521-3773 1433-7851 |
| Popis: | A method for the synthesis of benzylsilanes starting from the corresponding ammonium triflates is reported. Silyl boronic esters are employed as silicon pronucleophiles, and the reaction is catalyzed by copper(I) salts. Enantioenriched benzylic ammonium salts react stereospecifically through an SN2‐type displacement of the ammonium group to afford α‐chiral silanes with inversion of the configuration. A cyclopropyl‐substituted substrate does not undergo ring opening, thus suggesting an ionic reaction mechanism with no benzyl radical intermediate. SiR, the NMe has surrendered: Benzylic ammonium salts can be transformed into the corresponding silanes by a copper‐catalyzed SN2‐type displacement. The enantioenrichment of the precursors is completely retained in the α‐chiral silanes. A cyclopropyl group at the benzylic carbon atom remains intact, thereby supporting an ionic reaction mechanism. |
| Databáze: | OpenAIRE |
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