•Synthesis of 3-silylthiophenes possessing perfluoroalkyl groups on silicon atom.•Electropolymerization of 3-silylthiophenes with head-to-tail regioregularity.•Cyclic voltammogram of the polymers indicated both n- and p-doping properties.The synthesis of a novel class of 3-silyl substituted thiophenes possessing perfluoroalkyl groups on the silicon atom was investigated. The treatment of 3-bromothiophene with n-butyllithium followed by the reaction with halosilanes proceeded to afford the corresponding 3-silyl substituted thiophenes 1 in good yields. The chemical polymerization of the resulting 1 did not work well. However, the electropolymerization of 3-silylthiophenes 1a and 1b provided the corresponding polymers 5a and 5b with head-to-tail regioregularity. The cyclic voltammogram of the resulting polymers 5a and 5b indicated both n- and p-doping properties.Download high-res image (42KB)Download full-size image

•Highly fluorous ionic liquids have been synthesized.•Perfluoroalkyl groups were introduced in both anion and cation moieties.•Fluorophilicity was quantified by measurement of partition coefficients.The synthesis of a novel class of fluorous ionic liquids was investigated. The reaction of pyrrolidine or piperidine with perfluoroalkyl iodide in pyridine proceeded to give the corresponding tertiary amine derivatives 3 and 4 in good yields. The following reaction of the resulting compounds 3 and 4 with methyl iodide gave the corresponding iodide salts 5a and 6a in high yields. On the other hand, a similar reaction with an excess amount of perfluoroalkyl iodide afforded iodide salts 7a and 8a possessing two perfluoroalkyl groups on nitrogen atom. The anion exchange of the resulting iodides gave the ionic liquids with high fluorophilicity.Download high-res image (31KB)Download full-size image

The reaction of acylsilanes with α-sulfinyl carbanions such as α-lithioalkyl sulfoxide is described. The reaction proceeds to give silyl enol ethers preferentially through the initial formation of the α-silyl alkoxide intermediates. In particular, the products derived from enolizable acylsilanes were the regio-defined silyl enol ethers that cannot be obtained by usual enolization of the corresponding unsymmetrical ketones with base.

The reaction of 1-silylcyclopropyl anions with dichloromethyl methyl ether is described. The reaction with an excess amount of dichloromethyl methyl ether gives the corresponding cyclopropyl silyl ketones in low yields. On the other hand, the reaction under basic conditions proceeded smoothly to afford the corresponding cyclopropylidene derivatives, exclusively. The resulting cyclopropylidene compounds are subjected to hydrolysis or trapping with electrophiles easily to give the cyclopropyl silyl ketone derivatives in good yields.