Due to their structural rigidity, conjugation and unique bond torsion, sequence-specific arylethynylene and arylbutadiyne oligomers are excellent scaffolds for the study of shape-persistent supramolecular and nanoscale systems. With the ultimate goal of improving the generation of these important architectures, new synthetic methodologies have been developed utilizing an in situ ethynylsilane deprotection reaction. While synthetic strategies for the alkynylation of aryl moieties (Sonogashira) or the homocoupling of alkynes (Glaser) traditionally involve iterative pathways, the use of an in situ ethynylsilane deprotection reaction has been shown to allow for the rapid construction, often in one pot, of complex arylethynylene and arylbutadiyne oligomers. Key to the protocol is the inclusion of a mixture of amidine base, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), CuI and substoichiometric amounts of water. The use of trimethylsilylacetylene versus bis-trimethylsilylacetylene, base toggling, inclusion of dioxygen for homocoupling, sterics of silylacetylene protection and CO insertion projects will be discussed. 

Modified Sonogashira- and Glaser-type couplings: Reaction methodology for undergraduate research

248th National Meeting (2014)

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