Construction of Silicon-Containing Seven-Membered Rings by Catalytic [4 + 2 + 1] Cycloaddition through Rhodium Silylenoid
| Autor: | Ikuo Sasaki, Toshimichi Ohmura, Michinori Suginome |
|---|---|
| Rok vydání: | 2020 |
| Předmět: |
chemistry.chemical_classification
Diene 010405 organic chemistry Organic Chemistry Silylene chemistry.chemical_element Alkyne 010402 general chemistry 01 natural sciences Biochemistry Cycloaddition 0104 chemical sciences Catalysis Rhodium chemistry.chemical_compound Hydroboration chemistry Polymer chemistry Silylenoid Physical and Theoretical Chemistry |
| Zdroj: | Organic Letters. 22:2961-2966 |
| ISSN: | 1523-7052 1523-7060 |
| DOI: | 10.1021/acs.orglett.0c00690 |
| Popis: | A rhodium-catalyzed [4 + 2 + 1] cycloaddition involving 1,3-diene, alkyne, and silylene to afford silicon-containing seven-membered rings was established. In the presence of a rhodium catalyst bearing bis(diphenylphosphino)methane (DPPM), nona-1,3-dien-8-yne derivatives reacted efficiently at 80-110 °C with boryl(isopropoxy)silane or boryl(diethyamino)silane, which reacts as the synthetic equivalent of silylene, to afford 1-silacyclohepta-2,5-dienes (2,5-dihydro-1H-silepines). Regiodivergent and chemo- and stereoselective functionalization of the seven-membered nonconjugated diene was achieved by hydroboration mediated by Cs2CO3 or an iridium catalyst. |
| Databáze: | OpenAIRE |
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