The structure and absolute configuration of the antibiotic aphidicolin: a tetracyclic diterpenoid containing a new ring system

Dalziel, W.; Hesp, Barrie; Stevenson, Karen M.; Jarvis, John A. J.

doi:10.1039/p19730002841

Cited by 121 publications

(66 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…1) [10][11][12] have been isolated from plants. Similarly, fungal GAs, 13) aphidicolin (a specific inhibitor of DNA polymerase ), 14,15) and fusicoccin A (a diterpene glucoside that acts as a plant plasma membrane H þ -ATPase activator) 16,17) have been isolated from fungi. The cyclic carbon skeletons of these diterpenoids are elaborated from a common precursor, GGDP, and the formation of the cyclic hydrocarbons is catalyzed by specific diterpene cyclases.…”

mentioning

confidence: 99%

Recent Advances Regarding Diterpene Cyclase Genes in Higher Plants and Fungi

Toyomasu

2008

Bioscience, Biotechnology, and Biochemistry

100

View full text Add to dashboard Cite

Cyclic diterpenoids are commonly biosynthesized from geranylgeranyl diphosphate (GGDP) through the formation of carbon skeletons by specific cyclases and subsequent chemical modifications, such as oxidation, reduction, methylation, and glucosidation. A variety of diterpenoids are produced in higher plants and fungi. Rice produces four classes of diterpene phytoalexins, phytocassanes A to E, oryzalexins A to F, oryzalexin S, and momilactones A and B. The six diterpene cyclase genes involved in the biosynthesis of these phytoalexins were identified and characterized. Fusicoccin A was produced by the phytopathogenic Phomopsis amygdali and served as a plant H þ -ATPase activator. A PaFS, encoding a fungal diterpene synthase responsible for fusicoccin biosynthesis, was isolated. The PaFS is an unusual chimeric diterpene synthase that possesses not only terpene cyclase activity (the formation of fusicoccadiene, a biosynthetic precursor of fusicoccin A), but also prenyltransferase activity (the formation of GGDP). Thus, we identified a unique multifunctional diterpene synthase family in fungi.

show abstract

mentioning

confidence: 99%

Recent Advances Regarding Diterpene Cyclase Genes in Higher Plants and Fungi

Toyomasu

2008

Bioscience, Biotechnology, and Biochemistry

100

View full text Add to dashboard Cite

show abstract

“…The parent compounds of these classes are: (+)-aphidicolin (1), (+)-stemodin (2) and (+)-stemarin (3a) (Figure 1). (+)-Aphidicolin (1), which showed interesting biological properties, was isolated in 1972 from the fungus Cephalosporium aphidicola Petch [1,2]. (+)-Stemodin (2a) was isolated in 1973, along with (+)-stemodinone (2b), from Stemodia maritima L. [3].…”

Section: Aphidicolane Stemodane and Stemarane Diterpenoidsmentioning

confidence: 99%

(+)-Podocarpic Acid as Chiral Template in the Synthesis of Aphidicolane, Stemodane and Stemarane Diterpenoids †

et al. 2016

View full text Add to dashboard Cite

Abstract:In this review the synthetic work in the field of aphidicolane, stemodane and stemarane diterpenoids, in which readily available (+)-podocarpic acid (4) was used as chiral template for the construction of their polycyclic structures, is described as it developed along the years. In the frame of this work (+)-podocarpic acid (4) was a very useful tool in a model study leading to the syntheses of tetracyclic ketones 7 and 8, models of key intermediates 5a and 6 in the syntheses of (+)-aphidicolin (1) and (+)-stemodin (2a), respectively. (+)-Podocarpic acid (4) was also converted into (+)-2-deoxystemodinone (2d), allowing confirmation of the stemodane diterpenoids absolute configuration, into (+)-aphidicol-15-ene (36) and into Stemodia chilensis tetracyclic diterpenoid (+)-19-acetoxystemodan-12-ol (2f), allowing confirmation of its structure. (+)-Podocarpic acid (4) was then extensively used in the work which led to the synthesis of (+)-stemar-13-ene (57) and (+)-18-deoxystemarin (3b). Finally, (+)-4 was converted into (+)-2-deoxyoryzalexin S (66), which made it possible to demonstrate that the structure of (+)-66 could not be attributed to a Chilean Calceolaria isolated diterpenoid to which this structure had been assigned.

show abstract

“…This concept was an efficient feature of total syntheses of stemarin (1)(1), and of 2-desoxystemodinone (2a) and stemodinol (2b)(2,3); we now wish to describe its application to a stereospecific synthesis of (+)-aphidicol-15-ene (5), a derivative of aphidicolin (3) (4).' This synthesis was undertaken as a model, relative to a projected total synthesis of aphidicolin.…”

Section: -Hydroxybicyclo[222]octan-2-one System Represented Bymentioning

confidence: 99%

“…This intermediate, prepared from podocarpic acid (3), is the enantiomer represented by 6 and leads to the enantiomer 5 derived from aphidicolin (4).…”

Section: -Hydroxybicyclo[222]octan-2-one System Represented Bymentioning

confidence: 99%

A synthesis of (+)-aphidicol-15-ene

Kelly¹,

Lal²,

Gowda³

et al. 1984

Can. J. Chem.

View full text Add to dashboard Cite

A stereospecific synthesis of (+)-aphidicol-15-ene is described. Pursuing a concept successfully applied to our total synthesis of stemarin and the stemodane diterpenoids, the C/D ring system was elaborated by functional group manipulation and rearrangement of a 6-hydroxybicyclo[2.2.2]octan-2-one system. RONALD B. KELLY, G. SANKAR LAL, GOPALA GOWDA et RABINDRA N. Rw. Can. J. Chem. 62, 1930Chem. 62, (1984. This concept was an efficient feature of total syntheses of stemarin (1)(1), and of 2-desoxystemodinone (2a) and stemodinol (2b)(2,3); we now wish to describe its application to a stereospecific synthesis of (+)-aphidicol-15-ene (5), a derivative of aphidicolin (3)(4).' This synthesis was undertaken as a model, relative to a projected total synthesis of aphidicolin.The keto alcohol 6, formerly encountered as an intermediate in our synthesis of (+)-2-desoxystemodinone (2a)(3), served also as an intermediate in the present synthesis. This intermediate, prepared from podocarpic acid (3), is the enantiomer represented by 6 and leads to the enantiomer 5 derived from aphidicolin (4).In preparation for the rearrangement of the bicyclic system of 6 to that of 5, it was necessary to reduce the secondary hydroxyl group to a methylene group and convert the keto

show abstract

The structure and absolute configuration of the antibiotic aphidicolin: a tetracyclic diterpenoid containing a new ring system

Cited by 121 publications

References 0 publications

Recent Advances Regarding Diterpene Cyclase Genes in Higher Plants and Fungi

Recent Advances Regarding Diterpene Cyclase Genes in Higher Plants and Fungi

(+)-Podocarpic Acid as Chiral Template in the Synthesis of Aphidicolane, Stemodane and Stemarane Diterpenoids †

A synthesis of (+)-aphidicol-15-ene

Contact Info

Product

Resources

About