Synthesis of silylated polycyclic aromatic hydrocarbons by lithium-mediated mechanochemical Birch reductive silylation† † Dedicated to the memory of Dr Kazuhiko Sato at the National Institute of Advanced Industrial Science and Technology (AIST), Japan, in recognition of his outstanding contributions to silicon chemistry and catalysis, and in mourning of his untimely passing.
- 1Department of Chemistry, Graduate School of Science, Nagoya University Chikusa Nagoya 464-8602 Japan
Abstract
Silicon-substituted polycyclic aromatic hydrocarbons (Si-PAHs) are important functional π-conjugated molecules, but their synthesis is still largely dependent on the multistep preparation of precursors, such as halogenated PAHs. Herein, we report a lithium-mediated mechanochemical Birch reductive silylation of unfunctionalized PAHs in air at room temperature. Various silylated PAHs (Si-PAHs) and hydrogenated analogues were obtained directly from unfunctionalized PAHs by ball-milling PAHs with bulk Li(0) in a small amount of THF additive, followed by treatment with chlorosilanes, fluorosilanes, or hydrosilanes. This method accommodates a range of PAHs, including chrysene, fluoranthene, and perylene derivatives, and enables access to various substitution patterns that are difficult to achieve using conventional synthetic methods. The resulting Si-PAHs exhibit enhanced solubility and fluorescent quantum yields, along with a characteristic red shift in absorption and emission. Furthermore, the combination of the previously developed Li(0)-mediated mechanochemical cyclodehydrogenation and Birch reductive arylation with the present silylation enabled one-pot access to more complicated functional Si-PAHs.
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BibTeX
@article{mikawa2026synthesis,
title = {{Synthesis of silylated polycyclic aromatic hydrocarbons by lithium-mediated mechanochemical Birch reductive silylation† † Dedicated to the memory of Dr Kazuhiko Sato at the National Institute of Advanced Industrial Science and Technology (AIST), Japan, in recognition of his outstanding contributions to silicon chemistry and catalysis, and in mourning of his untimely passing.}},
author = {Shota Mikawa and Yoshifumi Toyama and Hideto Ito},
journal = {Chemical science},
year = {2026},
month = nov,
doi = {10.1039/d6sc05649k},
url = {https://europepmc.org/article/PMC/PMC13725590},
note = {CC BY-NC},
}
RIS
TY - JOUR
TI - Synthesis of silylated polycyclic aromatic hydrocarbons by lithium-mediated mechanochemical Birch reductive silylation† † Dedicated to the memory of Dr Kazuhiko Sato at the National Institute of Advanced Industrial Science and Technology (AIST), Japan, in recognition of his outstanding contributions to silicon chemistry and catalysis, and in mourning of his untimely passing.
AU - Shota Mikawa
AU - Yoshifumi Toyama
AU - Hideto Ito
PY - 2026
DA - 2026/11/02
JO - Chemical science
DO - 10.1039/d6sc05649k
UR - https://europepmc.org/article/PMC/PMC13725590
AB - Silicon-substituted polycyclic aromatic hydrocarbons (Si-PAHs) are important functional π-conjugated molecules, but their synthesis is still largely dependent on the multistep preparation of precursors, such as halogenated PAHs. Herein, we report a lithium-mediated mechanochemical Birch reductive silylation of unfunctionalized PAHs in air at room temperature. Various silylated PAHs (Si-PAHs) and hydrogenated analogues were obtained directly from unfunctionalized PAHs by ball-milling PAHs with bulk Li(0) in a small amount of THF additive, followed by treatment with chlorosilanes, fluorosilanes, or hydrosilanes. This method accommodates a range of PAHs, including chrysene, fluoranthene, and perylene derivatives, and enables access to various substitution patterns that are difficult to achieve using conventional synthetic methods. The resulting Si-PAHs exhibit enhanced solubility and fluorescent quantum yields, along with a characteristic red shift in absorption and emission. Furthermore, the combination of the previously developed Li(0)-mediated mechanochemical cyclodehydrogenation and Birch reductive arylation with the present silylation enabled one-pot access to more complicated functional Si-PAHs.
SN - 2041-6520
SN - 2041-6539
ER -