Synthetic transformation of hydroxymatairesinol from Norway spruce (Picea abies) to 7-hydroxysecoisolariciresinol, (+)-lariciresinol and (+)-cyclolariciresinol

Abstract

We have developed a method for the transformation of hydroxymatairesinol to optically pure (+)-lariciresinol and (+)-cyclolariciresinol via the hitherto unreported lignan 7-hydroxysecoisolariciresinol. The two naturally occurring isomers of hydroxymatairesinol were reduced with LiAlH₄ to a mixture of two epimers of 7-hydroxysecoisolariciresinol, which were further selectively transformed to (+)-lariciresinol and (+)-cyclolariciresinol by an acid catalysed intramolecular cyclisation reaction. The structure of the major isomer of 7-hydroxysecoisolariciresinol was confirmed by X-ray crystallography and thereby also the absolute configurations of the two isomers of hydroxymatairesinol were unambiguously proven. Optical purities were determined by chiral HPLC-MS/MS and optical rotation measurements.