Biosynthesis of Cytochalasans. Part 4. The mode of incorporation of common naturally‐occurring carboxylic acids into cytochalasin D

Vederas, John C.; Graf, Werner; David, L.; Tamm, Christoph

doi:10.1002/hlca.19750580704

Cited by 28 publications

(12 citation statements)

References 25 publications

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“…[2-14C]Octadecanal was synthesized by two cycles of nitrile elongation using a microscale adaptation of the method of Vederas et al (14), followed by LiAlH4 reduction of the resulting acid and reoxidation of the alcohol to the aldehyde. [1-3H]Octadecanal was synthesized by reduction of methyl octadecanoate with LiAl3H4, followed by oxidation of the resulting alcohol with pyridinium chlorochromate as indicated above.…”

Section: Methodsmentioning

confidence: 99%

Alkane biosynthesis by decarbonylation of aldehydes catalyzed by a particulate preparation from Pisum sativum.

Cheesbrough¹,

Kolattukudy²

1984

Proc. Natl. Acad. Sci. U.S.A.

166

137

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Mechanism of enzymatic conversion of a fatty acid to the corresponding alkane by the loss of the carboxyl carbon was investigated with particulate preparations from Pisum sativum. A heavy particulate preparation (sp. gr., 1.30 g/cm3) isolated by two density-gradient centrifugation steps catalyzed conversion of octadecanal to heptadecane and CO.Experiments with [1-3H,1_14C]octadecanal showed the stoichiometry of the reaction and retention of the aldehydic hydrogen in the alkane during this enzymatic decarbonylation. This decarbonylase showed an optimal pH of 7.0 and a Km of 35 ,uM for the aldehyde. This enzyme was severely inhibited by metal ion chelators and showed no requirement for any cofactors. Microsomal preparations and the particulate fractions from the first density-gradient step catalyzed acyl-CoA reduction to the corresponding aldehyde. Electron microscopic examination showed the presence of fragments of cell wall/cuticle but no vesicles in the decarbonylase preparation. It is concluded that the aldehydes produced by the acyl-CoA reductase located in the endomembranes of the epidermal cells are converted to alkanes by the decarbonylase located in the cell wall/cuticle region.Alkanes are widely distributed in the plant and animal kingdoms (1). Biological hydrocarbons usually have an odd number of carbon atoms, suggesting that they are derived by the loss of one carbon atom from fatty acids with even numbers of carbon atoms. Experiments with higher plant tissue slices strongly suggested that hydrocarbons are formed by chain elongation of fatty acids followed by loss of the carboxyl carbon, presumably by decarboxylation (2, 3). Subsequent work with insects (4) and mammals (5) supported this mechanism for alkane biosynthesis. Experiments with cell-free preparations from pea leaves showed that oxygen and ascorbate were required for the conversion of C32 fatty acid to alkane and that metal ion chelators strongly inhibited alkane synthesis (6). Subsequent studies showed that a major part of this alkane-generating activity was located in a crude microsomal fraction and that C18 to C32 fatty acids could serve as substrates for alkane formation (7). All of these substrates gave rise to mainly alkanes containing two carbon atoms less than the parent acid. Evidence was presented suggesting that in vitro the aldehyde generated from the parent acid by the classical a-oxidation was the immediate precursor of the alkane, whereas in vivo aldehydes generated by acyl-CoA reductase might be the immediate precursor of alkanes. It was suggested that the aldehyde might be decarborlylated to alkane. In the present paper, we describe the isolation of a particulate fraction devoid of a-oxidation activity, and we present direct experimental evidence for enzymatic decarbonylation of an aldehyde to alkane. MATERIALS AND METHODS Materials

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Section: Methodsmentioning

confidence: 99%

Alkane biosynthesis by decarbonylation of aldehydes catalyzed by a particulate preparation from Pisum sativum.

Cheesbrough¹,

Kolattukudy²

1984

Proc. Natl. Acad. Sci. U.S.A.

166

137

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“…. [25,26] Biosynthetic Diels-Alder Reactions [30,31] propionate, [30,31] methionine, [31,32] phenylalanine, [33] and tryptophan [31] as biosynthetic precursors to the cytochalasans. The perhydroisoindole group of cytochalasin A (50) and B (51) is thought to arise through an endo-selective intramolecular Diels-Alder reaction (Scheme 11).…”

Section: Cytochalasansmentioning

confidence: 99%

Chemistry and Biology of Biosynthetic Diels–Alder Reactions

2003

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Nature's repertoire of biosynthetic transformations has recently been recognized to include the Diels-Alder cycloaddition reaction. Evidence now exists that there are enzymes that mediate the Diels-Alder reaction in secondary metabolic biosynthetic pathways. 2002 marked the 100th anniversary of Alder's birth and 75 years since the discovery of the Diels-Alder reaction. It would appear that living systems discovered and made use of this ubiquitously useful ring-forming reaction eons ago for the construction of complex natural products. In this Review an overview is given of all of the known classes of natural products (polyketides, isoprenoids, phenylpropanoids, alkaloids) that have been speculated to arise by a biological Diels-Alder reaction.

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“…In extension of this work it was shown that (361) was transformed into triols (363) and (364) (118). A revised structure 33.2 (365) (366) was proposed for ent-16-kauren-19-o1 (366), extracted from coffee (120). 13C chemical shifts are given for one representative (365) (119).…”

Section: References Pp 195-229mentioning

confidence: 99%

The Use of Carbon-13 Nuclear Magnetic Resonance Spectroscopy in Natural Products Chemistry

Wehrli

Nishida²

1979

Fortschritte Der Chemie Organischer Naturstoffe / Progress in the Chemistry of Organic Natural Products

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Biosynthesis of Cytochalasans. Part 4. The mode of incorporation of common naturally‐occurring carboxylic acids into cytochalasin D

Cited by 28 publications

References 25 publications

Alkane biosynthesis by decarbonylation of aldehydes catalyzed by a particulate preparation from Pisum sativum.

Alkane biosynthesis by decarbonylation of aldehydes catalyzed by a particulate preparation from Pisum sativum.

Chemistry and Biology of Biosynthetic Diels–Alder Reactions

The Use of Carbon-13 Nuclear Magnetic Resonance Spectroscopy in Natural Products Chemistry

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