Synthesis and Stereochemical Characterization of Optically Active 1,2-Diarylethane-1,2-diols: Useful Chiral Controllers in the Ti-mediated Enantioselective Sulfoxidation

The series of phenylsubstituted 1,2-diphenylethane-1,2-diols 2a–h was prepared in high chemical (70–80%) and optical yields (∼90%) by Sharpless syn-dihydroxylation of the corresponding (E)-1,2-diarylethenes, in turn obtained by McMurry or Wittig reactions. The enantiomeric excesses of the samples were determined by HPLC analysis using Chiralcel OD chiral stationary phase (CSP). This CSP was able to resolve all the diols, except for 2g, with values ranging between 1.10–1.64. In all cases the (R,R) antipode was eluted first. (R,R) absolute configuration was assigned to the dextrorotatory (CHCl3) diols 2a–h by analyzing the CD spectra of their 2,2-dimethyl-1,3-dioxolanes 3a–h. In fact, the CD spectra of all these dioxolanes present a positive couplet (210–180 nm range) which can be nonempirically related to an (R,R) absolute configuration of the two stereocenters. Chirality 13:258–265, 2001. © 2001 Wiley-Liss, Inc.