Biosynthesis of the diterpene verrucosan-2β-ol in the phototrophic Eubacterium Chloroflexus aurantiacus -: A retrobiosynthetic NMR study

被引:29
作者
Rieder, C
Strauss, G
Fuchs, G
Arigoni, D
Bacher, A
Eisenreich, W
机构
[1] Tech Univ Munich, Inst Organ Chem & Biochem, D-85747 Garching, Germany
[2] Univ Freiburg, Fac Biol, Dept Microbiol, D-79104 Freiburg, Germany
[3] ETH Zurich, Organ Chem Lab, CH-8092 Zurich, Switzerland
关键词
D O I
10.1074/jbc.273.29.18099
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
The biosynthesis of verrucosan-2 beta-ol in the green phototrophic eubacterium Chloroflexus aurantiacus was investigated by in vivo incorporation of singly or doubly C-13-labeled acetate, The C-13 labeling of the isolated diterpene was analyzed by one- and two-dimensional NMR spectroscopy. The C-13-labeling patterns of verrucosan-2 beta-ol were compared with the labeling patterns of intermediary metabolites (acetyl-CoA, pyruvate, and glyceraldehyde 3-phosphate) which were deduced from amino acids and nucleosides by retrobiosynthetic analysis. The results show that verrucosan-2 beta-ol is synthesized via mevalonate and not via the deoxyxylulose pathway, which was discovered recently in some eubacteria, algae, and plants. A scheme for the formation of the unusual tetracyclic ring system is offered. The cyclization process is initiated by the solvolysis of pyrophosphate from geranyllinaloyl pyrophosphate and the mechanism involves a Wagner-Meerwein rearrangement, a 1,5-hydride shift, and a cyclopropylcarbinyl to cyclopropylcarbinyl rearrangement.
引用
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页码:18099 / 18108
页数:10
相关论文
共 44 条
[1]   ZUR BIOGENESE PENTAZYKLISCHER TRITERPENE IN EINER HOHEREN PFLANZE [J].
ARIGONI, D .
EXPERIENTIA, 1958, 14 (04) :153-155
[2]   Terpenoid biosynthesis from 1-deoxy-D-xylulose in higher plants by intramolecular skeletal rearrangement [J].
Arigoni, D ;
Sagner, S ;
Latzel, C ;
Eisenreich, W ;
Bacher, A ;
Zenk, MH .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1997, 94 (20) :10600-10605
[3]  
ARIGONI D, 1968, Pure and Applied Chemistry, V17, P331, DOI 10.1351/pac196817030331
[4]   STUDIES IN RELATION TO BIOSYNTHESIS .29. TERPENOID CHAIN OF MYCELIANAMIDE [J].
BIRCH, AJ ;
WINTER, J ;
KOCOR, M ;
SHEPPARD, N .
JOURNAL OF THE CHEMICAL SOCIETY, 1962, (APR) :1502-&
[5]   BIOLOGICAL SYNTHESIS OF CHOLESTEROL [J].
BLOCH, K .
SCIENCE, 1965, 150 (3692) :19-&
[6]  
Broers STJ, 1994, THESIS EIDGENOSSISCH
[8]  
CANONICA L, 1967, TETRAHEDRON LETT, P4657
[9]  
Cartayrade A., 1994, 2 S EUR NETW PLANT T
[10]  
DAUBEN WG, 1967, TETRAHEDRON LETT, P1735