Synthesis of the first pentaethynylferrocene derivatives

Starting from a bisprotected ferrocene-1,2,3-triscarbaldehyde, Ohira-alkynylation and Pd-catalyzed protection of the free alkyne with 4-iodotoluene leads to a ferrocene in which one Cp-ring is 1,2,3-substituted by two acetal rings (1,2-position) and an internal alkyne. Metalation of the ferrocene nucleus with sec-BuLi, workup with DMF and reduction with LiAlH4 leads to a 1,2,3,4-tetrasubstituted ferrocene carrying a hydroxymethyl group. The acetal groups are removed by para-toluenesulfonic acid and the aldehyde groups are converted into arylalkynes. A second metalation followed by workup with DMF furnishes a 1,2,3,4,5-pentasubstituted ferrocenecarbaldehyde. The aldehyde is transformed into an alkyne by the Ohira method and converted to an internal alkyne by Pd-catalyzed reaction with 4-iodotoluene. The sequence gives a 1,2,3,4,5-pentasubstituted ferrocene derivative with four alkyne groups and one hydroxymethyl group. Airless Marko oxidation of the alcohol is followed by another Ohira alkynylation. Pd-catalyzed arylation finishes the reaction sequence to give the symmetrical 1,2,3,4,5-pentakis(4′-tolylethynyl)ferrocene, the first pentaethynylferrocene derivative. A second, similar route was explored that furnished 1,2,3,4,5-pentakis(4′-butylphenylethynyl)ferrocene and its butadiyne-bridged dimer.