Synthesis and structural analysis of sterically hindered chiral 1,4-diol ligands derived from the lignan hydroxymatairesinol

The readily available natural lignan hydroxymatairesinol was transformed into sterically hindered and optically pure diphenyl, di-2-naphthyl, and tetramethyl 1,4-diol derivatives via arylation/alkylation of the aryltetralinbutyrolactone lignan (−)-conidendrin. In addition, the diastereoselective formation of stable hemiketals from the highly substituted butyrolactone was studied in detail. The conformations of the molecules prepared were studied computationally at molecular mechanics (MM), Hartree-Fock (HF)/6-31G∗, and (DFT/B3LYP/TZVP) levels including entropy contributions and by NMR-spectroscopy. The conformations adopted showed that these novel chiral 1,4-diols may be suitable as chiral ligands for the development of new chiral transition metal and organo catalysts.