The Asymmetric Synthesis of the [D8]-Labeled (−)-(S)-Dihydroxyverbacine, the Terminal Precursor in the Biogenesis of the Macrobicyclic Spermine Alkaloids Aphelandrine and Orantine

Nezbedová, Lenka; Drandarov, Konstantin; Werner, Christa; Hesse, Manfred

doi:10.1002/1522-2675(20001108)83:11<2953::aid-hlca2953>3.0.co;2-i

Cited by 8 publications

(2 citation statements)

References 10 publications

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“…To answer the question of whether (S)-dihydroxyverbacine (3) is indeed the correct proposed precursor for the enzymatic macrocyclization, (D 8 )-labeled (S)-dihydroxyverbacine (7) had to be synthesized (NezbedovaÂ et al 2000) and was used as a substrate.…”

Section: Resultsmentioning

confidence: 99%

“…The syntheses of the unlabeled (3) and (D 8 )-labeled precursor (S)-dihydroxyverbacine (7) were performed according to the method of NezbedovaÂ et al (2000). The identities of the target precursors were con®rmed by MS, 1 H-nuclear magnetic resonance (NMR), 13 C-NMR, and by two-dimensional NMR [total correlation spectroscopy (TOCSY); heteronuclear single quantum correlation (HSQC); heteronuclear multibond correlation (HMBC)].…”

Section: Synthesis Of Substratesmentioning

confidence: 99%

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Phenol oxidative coupling in the biogenesis of the macrocyclic spermine alkaloids aphelandrine and orantine in Aphelandra sp.

Nezbedová¹,

Hesse²,

Drandarov³

et al. 2001

Planta

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A crucial step in the biosynthesis of the spermine alkaloid aphelandrine and its diastereoisomer orantine is an intramolecular cyclization of the intermediate (S)-dihydroxyverbacine. In order to elucidate this step of the biosynthetic pathway, microsomes from the roots of Aphelandra squarrosa Nees were incubated with unlabeled and (D8)-labeled (S)-dihydroxyverbacine. It was shown that the microsomal fraction catalyzes the intramolecular coupling of (S)-dihydroxyverbacine to aphelandrine. This was proven by microsomal transformation of (D8)-labeled (S)-dihydroxyverbacine to (D8)-labeled aphelandrine. The reaction absolutely requires NAPDH and O2. The underlying reaction mechanism is probably an oxidative phenol coupling catalyzed by an aphelandrine synthase. This enzyme is proposed to be a cytochrome P-450 oxidase. The intramolecular cyclization of (S)-dihydroxyverbacine represents an important point in the biogenesis of the aphelandrine-type alkaloids.

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Section: Resultsmentioning

confidence: 99%

Section: Synthesis Of Substratesmentioning

confidence: 99%

Phenol oxidative coupling in the biogenesis of the macrocyclic spermine alkaloids aphelandrine and orantine in Aphelandra sp.

Nezbedová¹,

Hesse²,

Drandarov³

et al. 2001

Planta

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An Improved and Versatile Method for the Rapid Synthesis of Aryldihydrobenzofuran Systems by a Boron Tribromide‐Mediated Cyclization Reaction

Detterbeck

Hesse

2003

Helvetica Chimica Acta

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Boron tribromide is presented as a highly reactive reagent that simultaneously allows the demethylation and fully diastereoselective cyclization of different precursor molecules, obtained by an aldol‐type reaction, to a series of hydroxylated aryldihydrobenzofuran systems in racemic form. The latter are often found as key structures in natural compounds of different classes. Syntheses of educts, which mainly took advantage of a versatile Rieche formylation, are also described.

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New reagent for oxidative phenol coupling. The transformation of the monocyclic spermine base (S)-dihydroxyverbacine to the bicyclic alkaloid (S,S,S)-aphelandrine by cell free extract of barley seedlings

Nezbedová

Hesse

Drandarov

et al. 2001

Tetrahedron Letters

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The Asymmetric Synthesis of the [D8]-Labeled (−)-(S)-Dihydroxyverbacine, the Terminal Precursor in the Biogenesis of the Macrobicyclic Spermine Alkaloids Aphelandrine and Orantine

Cited by 8 publications

References 10 publications

Phenol oxidative coupling in the biogenesis of the macrocyclic spermine alkaloids aphelandrine and orantine in Aphelandra sp.

Phenol oxidative coupling in the biogenesis of the macrocyclic spermine alkaloids aphelandrine and orantine in Aphelandra sp.

An Improved and Versatile Method for the Rapid Synthesis of Aryldihydrobenzofuran Systems by a Boron Tribromide‐Mediated Cyclization Reaction

New reagent for oxidative phenol coupling. The transformation of the monocyclic spermine base (S)-dihydroxyverbacine to the bicyclic alkaloid (S,S,S)-aphelandrine by cell free extract of barley seedlings

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