On the stereoselective synthesis of (+)-pinoresinol in Forsythia suspensa from its achiral precursor, coniferyl alcohol.
The residue from Forsythia suspensa stems, upon removal of soluble enzymes, has provided the first evidence for a stereoselective coupling enzyme in lignan biosynthesis.  This preparation catalyses the preferred formation (ca 65%) of (+)-[8,8'-14C]pinoresinol from [8-14C]coniferyl alcohol in the absence of exogenously provided cofactors; addition of H2O2 had little effect on enantiomeric composition.  However, when NAD and malate were supplied, the stereoselectivity of the coupling reaction was significantly enhanced and pinoresinol consisting of ca 80% of the (+)-antipode was obtained.  Clearly, the insoluble residue contains a specific coupling enzyme which catalyses (+)-pinoresinol formation from coniferyl alcohol.  By contrast, when [8-14C]sinapyl alcohol was employed as substrate, only racemic syringaresinols were formed:  this non-stereoselective peroxidase-catalysed coupling reaction presumably accounts for the low levels of (-)-pinoresinol encountered in this system when coniferyl alcohol is used as a substrate.
Davin
L B
LB
Institute of Biological Chemistry, Washington State University, Pullman 99164-6340.
Bedgar
D L
DL
Katayama
T
T
Lewis
N G
NG
D006861:Hydrogen Peroxide / Q000494:pharmacology; D017705:Lignans / Q000096:biosynthesis / Q000737:chemistry / Q000378:metabolism*; D008291:Malate Dehydrogenase / Q000378:metabolism; D008293:Malates / Q000494:pharmacology; D009243:NAD / Q000494:pharmacology; D010544:Peroxidases / Q000378:metabolism; D010636:Phenols / Q000378:metabolism*; D010936:Plant Extracts / Q000737:chemistry / Q000378:metabolism*; D010944:Plants / Q000201:enzymology / Q000378:metabolism*; D013237:Stereoisomerism
D017705:Lignans; D008293:Malates; D010636:Phenols; D010936:Plant Extracts; D009243:NAD; D006861:Hydrogen Peroxide; C010559:coniferyl alcohol; D008291:Malate Dehydrogenase; D010544:Peroxidases