Biomimetic Synthesis of Equisetin and (+)-Fusarisetin A
(+)‐Fusarisetin A belongs to a group of acyl tetramic acid natural products that show potential anticancer activity. Equisetin, a biogenetically related acyl tetramic acid, contains the basic skeleton of (+)‐fusarisetin A. We proposed that equisetin and (+)‐fusarisetin A share a biosynthetic pathway...
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Published in | Chemistry : a European journal Vol. 19; no. 39; pp. 13040 - 13046 |
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Main Authors | , , , , , |
Format | Journal Article |
Language | English |
Published |
Weinheim
WILEY-VCH Verlag
23.09.2013
WILEY‐VCH Verlag Wiley Wiley Subscription Services, Inc |
Subjects | |
Online Access | Get full text |
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Summary: | (+)‐Fusarisetin A belongs to a group of acyl tetramic acid natural products that show potential anticancer activity. Equisetin, a biogenetically related acyl tetramic acid, contains the basic skeleton of (+)‐fusarisetin A. We proposed that equisetin and (+)‐fusarisetin A share a biosynthetic pathway that starts with naturally occurring (S)‐serine and an unsaturated fatty acid. In support of this hypothesis, we have demonstrated that a cyclization sequence involving an intramolecular Diels–Alder reaction followed by a Dieckmann cyclization of polyenoylamino acid yielded equisetin. The aerobic oxidation of equisetin, promoted by either MnIII/O2 or a reactive oxygen species (ROS) produced by visible‐light chemistry, gave peroxyfusarisetin, which could be easily reduced to (+)‐fusarisetin A. We report herein detailed information on the biogenetic synthesis of equisetin and (+)‐fusarisetin A.
Make the change to bio! Biomimetic synthesis of equisetin and (+)‐fusarisetin A was achieved based on a biosynthetic hypothesis. An intramolecular Diels–Alder reaction followed by a Dieckmann cyclization of polyenoylamino ester furnished equisetin. The aerobic oxidation of equisetin to give (+)‐fusarisetin A was mediated by a MnIII/O2 system or reactive oxygen species (ROS) (see scheme). |
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Bibliography: | program for professor of special appointment - No. 1220000144 Shanghai "Pujiang Program" - No. 11PJ1402800 RFDP - No. 20110076120022 ArticleID:CHEM201302163 istex:44BB29600DA5D05567851E82AE2347BA45E882F4 ark:/67375/WNG-5LV418DF-8 NSFC - No. 21102045; No. 21272076 ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 0947-6539 1521-3765 |
DOI: | 10.1002/chem.201302163 |