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Updated: May 10, 2025

Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units
Published on: September 18, 2016
Cross-Dimerization Giving Silyl-Substituted Conjugated Hexatrienes: An Approach to 1,6-Diarylhexa-1,3,5-trienes
Fuma Sakamoto1, Eri Arata1, Ryo Saito1
1Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Nakacho, Koganei, Tokyo 184-8588, Japan.
Abstract:
A new approach to 1,6-diarylhexa-1,3,5-trienes (DAHs) has been achieved. Cross-dimerization of 1-aryl-2-silylethyne (1) with benzyl((E)-buta-1,3-dien-1-yl)dimethylsilane (2c) catalyzed by [Ru(η6-naphthalene)(η4-1,5-cycloocatdiene)] produces (1E,3E)-(6-aryl-5-silylhexa-1,3,5-trien-1-yl)benzyl(dimethyl)silane (3), where the dominant stereochemistry at the 5-position in 3 is the E-form. Subsequent Hiyama cross-coupling of 3 with aryl iodide catalyzed by [Pd2(dibenzylideneacetone)3]·C6H6 in the presence of TBAF·3H2O gives a series of (1E,3E,5E)-1,6-diarylhexa-1,3,5-trienes (DAH), showing that the C(5)═C(6) double bond rotates in the event of protodesilylation. The controlled experiments suggest that the Hiyama cross-coupling of the terminal silyl group in 3 takes place first, and then protodesilylation of the internal silyl group occurs to give (1E,3E,5E)-DAHs. An X-ray structure analysis reveals the molecular structure of (1E,3E,5E)-1-(4-acetylphenyl)-6-phenylhexa-1,3,5-triene. The photochemical study of some new DAHs has been conducted, showing bright fluorescence upon irradiation with a large Stokes shift (∼4026 cm-1) by π-π* transition according to TD-DFT calculations.
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