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Updated: May 28, 2025

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Synthesis of a dilithiobutadiene bearing extremely bulky silyl substituents and its reactivity toward functionalized
Katharina Münster1, Shunsuke Kudo1, Takuya Kuwabara1
1Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-okubo, Sakura-ku, Saitama-city, Saitama, 338-8570, Japan. masaichi@chem.saitama-u.ac.jp.
Abstract:
The synthesis and full characterization of 1,4-dilithio-1,4-bis(triisopropylsilyl)-2,3-diphenylbuta-1,3-diene (1b) are reported. This molecule featuring extremely bulky silyl groups at the 1- and 4-positions serves as a precursor for the synthesis of 2,5-bis(triisopropylsilyl)-3,4-diphenyl-1-silacyclopenta-1,3-dienes (siloles) bearing various substituents at the silicon atom (SiR2 = SiH2 (4), SiH(OMe) (5), SiF2 (6), SiBr2 (7), SiBr(OMe) (8)). Importantly, compounds 6 and 7 reacted with lithium to afford 2,5-bis(triisopropylsilyl)-3,4-diphenyldilithiosilole (9). The solid-state molecular structure and solution NMR spectra reveal the formation of an aromatic ring system, as opposed to the precursors 6 and 7, with two Li cations coordinated by the silacycle in η5-fashions. The sterically bulky dilithiosilole 9 can be applied as an important starting material in the pursuit of low-valent silicon species without donor stabilization.
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