Deprotonative Silylation of Aromatic C-H Bonds Mediated by a Combination of Trifluoromethyltrialkylsilane and Fluoride

Kanako Nozawa-Kumada , Sayuri Osawa , Midori Sasaki (1) , Isabelle Chataigner (2) , Masanori Shigeno , Yoshinori Kondo (2, 3)

1 Research Institute for Applied Mechanics, Kyushu University
2 COBRA - Chimie Organique et Bioorganique : Réactivité et Analyse
3 Tohoku University [Sendai]

A method for the deprotonative silylation of aromatic C–H bonds has been developed using trifluoromethyltrimethylsilane (CF3SiMe3, Ruppert–Prakash reagent) and a catalytic amount of fluoride. In this reaction, CF3SiMe3 is considered to act as a base and a silicon electrophile. This process is highly tolerant to various functional groups on heteroarenes and benzenes. Furthermore, this method can be applied to the synthesis of trimethylsilyl group-containing analogs of TAC-101, which is a bioactive synthetic retinoid with selective affinity for retinoic acid receptor α (RAR-α) binding. We also report further transformations of the silylated products into useful derivatives.

Domaines: Chimie

Kanako Nozawa-Kumada, Sayuri Osawa, Midori Sasaki, Isabelle Chataigner, Masanori Shigeno, et al.. Deprotonative Silylation of Aromatic C-H Bonds Mediated by a Combination of Trifluoromethyltrialkylsilane and Fluoride. Journal of Organic Chemistry, 2017, 82 (18), pp.9487-9496. ⟨10.1021/acs.joc.7b01525⟩. ⟨hal-02046303⟩