Reversible C-H bond silylation with a neutral silicon Lewis acid
The silicon-carbon bond is a valuable linchpin for synthetic transformations. However, installing Si-C functionalities requires metalated C-nucleophiles, activated silicon reagents (silylium ions, silyl radicals, and silyl anions), or transition metal catalysis, and it occurs irreversibly. In contra...
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| Main Authors: | , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
2023
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| In: |
Chemical science
Year: 2023, Volume: 14, Issue: 40, Pages: 11237-11242 |
| ISSN: | 2041-6539 |
| DOI: | 10.1039/D3SC03488G |
| Online Access: | Verlag, kostenfrei, Volltext: https://doi.org/10.1039/D3SC03488G Verlag, lizenzpflichtig, Volltext: https://pubs.rsc.org/en/content/articlelanding/2023/sc/d3sc03488g 
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| Author Notes: | Thaddäus Thorwart and Lutz Greb |
| Summary: | The silicon-carbon bond is a valuable linchpin for synthetic transformations. However, installing Si-C functionalities requires metalated C-nucleophiles, activated silicon reagents (silylium ions, silyl radicals, and silyl anions), or transition metal catalysis, and it occurs irreversibly. In contrast, spontaneous C-H silylations with neutral silanes leading to anionic silicates, and their reversible deconstruction, are elusive. Herein, the CH-bond silylation of heterocycles or a terminal alkyne is achieved by reaction with bis(perfluoro(N-phenyl-ortho-amidophenolato))silane and 1,2,2,6,6-pentamethylpiperidine. Computational and experimental insights reveal a frustrated Lewis pair (FLP) mechanism. Adding a silaphilic donor to the ammonium silicate products induces the reformation of the C-H bond, thus complementing previously known irreversible C-H bond silylation protocols. Interestingly, the FLP “activated” N-methylpyrrole exhibits “deactivated” features against electrophiles, while a catalytic functionalization is found to be effective only in the absence of a base. |
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| Item Description: | Veröffentlicht: 14. September 2023 Gesehen am 20.11.2023 |
| Physical Description: | Online Resource |
| ISSN: | 2041-6539 |
| DOI: | 10.1039/D3SC03488G |