23 ^<13>C-^<13>Cおよび^<13>C-^2H couplingを利用した生合成研究

概要

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Application of ^<13>C-NMR to biosynthetic studies has brought about new findings in the field of natural products such as vitamine B_<12>, polyketides, terpenoids and steroids. Especially, the use of multiple labelled precursors and the detection of ^<13>C-^<13>C coupling gave the infromation that, otherwise, could not be obtained. We will report here the results of our experiments carried out to clarify the scope and limitation of the use of ^<13>C-^<13>C coupling as well as ^<13>C-^2H coupling. The intact and stereospecific incorporation of malonate-[1,2,3-^<13>C_3] was demonstrated in cycloheximide(1) Scytalone(5) labelled by acetate-[1,2-^<13>C_2]showed the presence of two different mode of acetate arrangement as shown in 7 and 8, indicating 5 is biosynthesized via symmetrical intermediate(6). The effectiveness of acetate-[2-^<13>C,2-^2H_3] in tracing the fate of acetate hydrogen in polyketide biosynthesis was demonstrated in scytalone (5), (+)rugulosin(9) and 2-hexyl-5-propylresorcinol(12). Deuterium was not only incorporated into aromatic rings but also into methylenes of saturated alkyl chains. Double labelled acetate was also applied to biosynthesis of averufin(13) and sterigmatocystin (16), intermediates in aflatoxin biosynthesis, to clarify the chirality of ^2H labelling, as well as the mechanism of bisfuranoid ring formation.
天然有機化合物討論会の論文
1978-08-22