Selective monosulfoxidation of tetrathiafulvalenes into chiral TTF-sulfoxides.

Four inner tetrathiafulvalene-sulfoxides have been synthesized upon reaction of tetrathiafulvalene (TTF), tetramethyl-tetrathiafulvalene (TMTTF), tetrakis (thiomethyl)-tetrathiafulvalene (TMT-TTF), and bis(ethylenedithio)-tetrathiafulvalene (BEDT-TTF) with enantiopure (+) or (-)-(8,8-dichlorocamphorylsulfonyl)-oxaziridine as oxidizing agent. Chiral HPLC studies indicate very weak enantioselectivities for TTF-SO 3 and TMTTF-SO 4, formation of racemic mixture in the case of TMT-TTF-SO 5, and a rather good selectivity, up to 44% ee, in the case of BEDT-TTF-SO 1. The solid state structures of TMTTF-SO 4 and TMT-TTF-SO 5 have been determined by single crystal X-ray diffraction. Both compounds crystallize as racemates in the centrosymmetric triclinic space group P-1. Theoretical calculations at DFT/B3LYP/6-31+G* level afford optimized geometries in good accordance with the experimental structures and emphasize the participation of the chiral sulfoxide group in HOMO and LUMO. Time-dependent DFT calculations corroborated with electronic circular dichroism spectra allow the assignment of the absolute configuration (R) for the major enantiomer of 1 when the (+)-sulfonyl-oxaziridine is used as oxygen transfer reagent. Preliminary semipreparative HPLC separation provided enantioenriched fractions up to 63% ee.