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

• Published in: Journal of organic chemistry Vol. 82; no. 18; pp. 9487 - 9496
• Main Authors: Nozawa-Kumada, Kanako, Osawa, Sayuri, Sasaki, Midori, Chataigner, Isabelle, Shigeno, Masanori, Kondo, Yoshinori
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 15.09.2017; Amer Chemical Soc
• Subjects: Chemical Sciences; Chemistry; Chemistry, Organic; Fluorides - chemistry; Hydrocarbons, Fluorinated - chemistry; Molecular Structure; Physical Sciences; Protons; Science & Technology; Silanes - chemical synthesis; Silanes - chemistry; Trimethylsilyl Compounds - chemistry; FUNCTIONALIZATION; HETEROARENES; CROSS-COUPLING REACTION; RUPPERT-PRAKASH REAGENT; HYDROSILANES; PALLADIUM-CATALYZED SILYLATION; ONIUM AMIDE BASES; ARYL HALIDES; POTASSIUM TERT-BUTOXIDE; TERMINAL ALKYNES
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.7b01525

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.