Palladium-Catalyzed Skeletal Rearrangement of Substituted 2-Silylaryl Triflates via 1,5-C−Pd/C−Si Bond Exchange
Daigo Hayashi
Division of Chemistry, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531 Japan
Search for more papers by this authorDr. Tomohiro Tsuda
Division of Chemistry, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Ryo Shintani
Division of Chemistry, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531 Japan
Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871 Japan
Search for more papers by this authorDaigo Hayashi
Division of Chemistry, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531 Japan
Search for more papers by this authorDr. Tomohiro Tsuda
Division of Chemistry, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Ryo Shintani
Division of Chemistry, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531 Japan
Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871 Japan
Search for more papers by this authorGraphical Abstract
A palladium-catalyzed skeletal rearrangement of 2-(2-allylarylsilyl)aryl triflates has been developed to give tetrahydrophenanthrosiloles via 1,5-C−Pd/C−Si bond exchange. The reaction pathways can be switched by tuning the reaction conditions to give fused dihydrodibenzosilepin derivatives from the same starting materials. The inspection of the reaction conditions revealed the importance of carboxylates in promoting the C−Pd/C−Si bond exchange.
Abstract
A palladium-catalyzed skeletal rearrangement of 2-(2-allylarylsilyl)aryl triflates has been developed to give highly fused tetrahydrophenanthrosilole derivatives via unprecedented 1,5-C−Pd/C−Si bond exchange. The reaction pathways can be switched toward 4-membered ring-forming C(sp2)−H alkylation by tuning the reaction conditions to give completely different products, fused dihydrodibenzosilepin derivatives, from the same starting materials. The inspection of the reaction conditions revealed the importance of carboxylates in promoting the C−Pd/C−Si bond exchange.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.
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