Collect. Czech. Chem. Commun. 2004, 69, 2193-2211

Synthetic Studies Toward Chiral Aromatic Triynes as Key Substrates for the Asymmetric Synthesis of Helicene-Like Molecules

Zuzana Alexandrová, Irena G. Stará*, Petr Sehnal, Filip Teplý, Ivo Starý*, David Šaman and Pavel Fiedler

Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 166 10 Prague 6, Czech Republic


We have developed the synthesis of model nonracemic aromatic triynes (-)-(S)-1-4 containing the 1-{[2-(but-3-yn-1-yl)-1-naphthyl]ethynyl}-2-{[((S)-1-methylprop-2-yn-1-yl)oxy]- methyl}naphthalene unit. The common 1,2-di(2-substituted-1-naphthyl)acetylene part was constructed via Sonogashira coupling of appropriate 1-iodonaphthalenes with 1-ethynylnaphthalenes both bearing tethered acetylene units in positions 2. The chirality of triynes (-)-(S)-1-4 was introduced by incorporating commercially available (-)-(S)-but-3-yn-2-ol (10) into tethered acetylene units. The nonracemic triynes are intended to be used as substrates in stereoselective [2+2+2] triyne cycloisomerization catalyzed by transition metal complexes.

Keywords: Alkynes; Arenes; Chirality; Copper; Cross-coupling; Helical structures; Palladium; Synthesis design.

References: 36 live references.