Pinoresinol-Lariciresinol Reductases with Opposite Enantiospecificity Determine the Enantiomeric Composition of Lignans in the Different Organs of Linum usitatissimum L.[*]

Abstract

Lignans in higher plants represent an ideal class of natural products to be investigated for the origin of stereochemical diversity since chiral lignans occur in pure enantiomeric form as well as in enantiomeric mixtures. Seeds of Linum usitatissimum contain 8S, 8′S-(+)- and 8R, 8′R-(−)-secoisolariciresinol [SS-(+)- and RR-(−)-secoisolariciresinol, respectively] as diglucosides (SS- and RR-secoisolariciresinol diglucosides) whereas aerial parts of flowering L. usitatissimum accumulate only lignans derived from RR-(−)-secoisolariciresinol. Pinoresinol-lariciresinol reductase (PLR) catalyzes two early steps in lignan biosynthesis. Up to now, only a cDNA encoding a PLR (PLR‐Lu1) which is enantiospecific for the conversion of 8S, 8′S-(−)-pinoresinol (SS-pinoresinol) via 8S, 8′S-(−)-lariciresinol (SS-lariciresinol) to SS-(+)-secoisolariciresinol was cloned. Here we present the cloning of a cDNA encoding a RR-pinoresinol-RR-lariciresinol reductase (PLR‐Lu2) from the leaves of L. usitatissimum which converts only RR-pinoresinol to RR-secoisolariciresinol. In leaves and stems of L. usitatissimum accumulating the 8R, 8′R-enantiomers of lignans, only PLR‐Lu2 was transcriptionally active. Both PLR‐Lu1 and PLR‐Lu2 transcripts were observed in seeds and contribute to the synthesis of SS- and RR-secoisolariciresinol, respectively. Thus, the enantiomeric composition of lignans in the organs of L. usitatissimum appears to be determined by the relative action of two PLRs with opposite enantiospecificities rather than by a single enzyme of low enantiospecificity.

lignin - Linum - Linaceae - HPLC/UV/MS/CD - pinoresinol‐lariciresinol reductase - stereochemistry

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1 Dedicated to Prof. Dr. Wolfgang Barz on the occasion of his 75th birthday.