Synlett 2017; 28(18): 2460-2464
DOI: 10.1055/s-0036-1590835
© Georg Thieme Verlag Stuttgart · New York

Formal Nucleophilic Silyl Substitution of Aryl Halides with Silyllithium Reagents via Halogenophilic Attack of Silyl Nucleophiles

Eiji Yamamoto, Satoshi Ukigai, Hajime Ito*
  • Division of Applied Chemistry & Frontier Chemistry Center, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan   Email:
This work was financially supported by the NEXT (Japan) program (Strategic Molecular and Materials Chemistry through Innovative Coupling Reactions) of Hokkaido University. This work was also supported by JSPS KAKENHI Grant Numbers 15H03804, 15K13633, and 26·2447. E.Y. was supported by a Grant-in-Aid for JSPS Fellows.
Further Information

Publication History

Received: 09 May 2017

Accepted after revision: 20 June 2017

Publication Date:
24 July 2017 (eFirst)

Published as part of the Cluster Silicon in Synthesis and Catalysis


A new reaction has been developed for the formal nucleo­philic silyl substitution of aryl halides with silyllithium or silylpotassium reagents. Dimethylphenylsilyllithium reacted with various aryl halides to form the corresponding arylsilanes in moderate to good yields with concomitant formation of the disilanes under the optimized reaction conditions. Mechanistic studies indicated that this silyl substitution reaction progresses through polar halogenophilic attack of silyl nucleo­philes.

Supporting Information

  • References and Notes

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  • 11 Typical Procedure for Silyl Substitution Reaction with Silyllithium Reagent A vial with a screw cap and a silicon-coated rubber septum was connected to a vacuum/nitrogen manifold through a needle, and it was evacuated and refilled with nitrogen three times. Dimethylphenylsilyllithium (0.4 M in THF, 2.5 mL, 2.0 equiv) was added to the vial under nitrogen atmosphere. 1-Bromo-3,5-dimethylbenzene (93.5 mg, 0.51 mmol) was added to the vial, then stirred at 30 °C. After 1 h, the reaction mixture was analyzed by GC to check completeness of the reaction. When the reaction was complete, H2O was added and the mixture was extracted three times with Et2O. The organic layer was washed with water and the combined organic layer was then dried over MgSO4 followed by filtration and evaporation. The crude product was purified by silica-gel column chromatography with hexane eluent, then further purified by gel permeation chromatography to give 3da in 63% isolated yield (76.5 mg, 0.318 mmol). 1H NMR (392 MHz, CDCl3): δ = 0.53 (s, 6 H), 2.30 (s, 6 H), 7.01 (s, 1 H), 7.13 (s, 2 H), 7.30–7.38 (m, 3 H), 7.49–7.55 (m, 2 H). 13C NMR (99 MHz, CDCl3): δ = –2.3 (CH3), 21.4 (C), 127.7 (CH), 129.0 (CH), 130.9 (CH), 131.9 (CH), 134.2 (CH), 137.1 (C), 137.9 (C), 138.5 (C). HRMS (EI): m/z [M]+ calcd for C16H20Si: 240.13343; found: 240.13281.