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Synthesis of Hybrid Masked Triyne−Phenylene Axial Rods Containing (E)-β-Chlorovinylsilanes in the π-Conjugated Framework

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posted on 16.10.2009, 00:00 authored by Michael D. Weller, Benson M. Kariuki, Liam R. Cox
A two-directional synthesis of a masked hexayne 7, in which two β-chlorovinylsilanes protect two of the internal alkynes, is reported. The key step involves the Pd-catalyzed oxidative dimerization of alkyne 10 to provide diyne 12, which is elaborated into centrosymmetric masked hexayne 7 in four steps. Masked hexayne 7 is a constitutional isomer of masked hexayne 2, which has been used as a monomer unit for oligoyne assembly. Although masked hexayne 7 was not as convenient a building block as 2 for application in oligoyne assembly, one of its precursors, namely alkyne 10, could be used successfully in Sonogashira couplings, which allowed the incorporation of aromatic spacers and the formation of hybrid masked triyne-phenylenes 20 and 28. Compounds 20 and 28 both contain removable end-groups, which will permit their application as building blocks for the assembly of classes of long-chain, π-conjugated rod-like molecules. Rod-like molecule 34, which possesses a similar conjugated scaffold as 28, was also prepared by using a similar strategy. Treatment of 34 with TBAF effected a 2-fold dechlorosilylation to provide a rigid rod molecule 35 in which two phenylene units interrupt an octayne scaffold.