Biosynthesis of resorcylic acid lactone lasiodiplodin in Lasiodiplodia theobromae.
The biosynthesis of lasiodiplodin (1) and its (5S)-5-hydroxylated derivative (2) were investigated by the administration of (13)C-labeled acetates to Lasiodiplodia theobromae. The labeling patterns of biosynthetically (13)C-labeled 1 and 2 were determined by (13)C-NMR and INADEQUATE spectra, demonstrating the octaketide origins of 1 and 2. Taking into account the biosynthetic study of resorcylic acid lactones, the involvement of highly reduced acyl intermediates in the biosynthesis of lasiodiplodins was presumed; thus, we synthesized (2)H-labeled hypothetical acyl intermediates of 1, 9-hydroxydecanoic acid (4) and its N-acetylcysteamine thioester (SNAC, 5). When L. theobromae was incubated with 5 mM of a (2)H-labeled intermediate, the (2)H-label from the intermediate was incorporated at the expected position of 1. These incorporation studies revealed that 1 was produced via a pathway which closely resembles that of resorcylic acid lactone biosynthesis.
Division of Applied Bioscience, Research Faculty of Agriculture, Hokkaido University, Sapporo, Japan.
Takasumi
T
Kashima
Kosaku
K
Takahashi
Hideyuki
H
Matsuura
Kensuke
K
Nabeta
D000085:Acetates / Q000737:chemistry; D001203:Ascomycota / Q000378:metabolism*; D002247:Carbon Isotopes / Q000737:chemistry; D003903:Deuterium / Q000737:chemistry; D062385:Hydroxybenzoates / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D013194:Staining and Labeling; D015025:Zearalenone / Q000031:analogs & derivatives* / Q000096:biosynthesis / Q000737:chemistry
D000085:Acetates; D002247:Carbon Isotopes; D062385:Hydroxybenzoates; C417552:lasiodiplodin; D015025:Zearalenone; D003903:Deuterium