Synthesis of (±)- and (−)-botryodiplodin using stereoselective radical cyclizations of acyclic esters and acetals

Nouguier, R.; Gastaldi, Stéphane; Stien, Didier; Bertrand, M.; Villar, Félix; Andrey, Olivier; Renaud, Philippe

doi:10.1016/j.tetasy.2003.06.004

Cited by 32 publications

(17 citation statements)

References 53 publications

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“…(±)-Botryodiplodin (6) was extracted from the reaction mixture into dichloromethane and purified by chromatography on silica gel using ether:hexane 4:1 followed by re-chromatography on silica gel using dichloromethane:methanol 20:1 to yield 116 mg (20.9% overall yield) at a purity of >98% based on thin layer chromatography and nuclear magnetic resonance spectroscopy. The (±)-botryodiplodin (6) exhibited 1 H nuclear magnetic resonance spectroscopy values and thin layer chromatographic R f values identical to those reported in the literature [39,62] and those obtained in this laboratory with (−)-botryodiplodin purified from cultures of M. phaseolina [32], except that (±)-botryodiplodin was not optically active.…”

Section: Preparation Of (±)-Botryodiplodinsupporting

confidence: 81%

Phytotoxic Responses of Soybean (Glycine max L.) to Botryodiplodin, a Toxin Produced by the Charcoal Rot Disease Fungus, Macrophomina phaseolina

Abbas

Bellaloui

Butler

et al. 2020

Toxins

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Toxins have been proposed to facilitate fungal root infection by creating regions of readily-penetrated necrotic tissue when applied externally to intact roots. Isolates of the charcoal rot disease fungus, Macrophomina phaseolina, from soybean plants in Mississippi produced a phytotoxic toxin, (−)-botryodiplodin, but no detectable phaseolinone, a toxin previously proposed to play a role in the root infection mechanism. This study was undertaken to determine if (−)-botryodiplodin induces toxic responses of the types that could facilitate root infection. (±)-Botryodiplodin prepared by chemical synthesis caused phytotoxic effects identical to those observed with (−)-botryodiplodin preparations from M. phaseolina culture filtrates, consistent with fungus-induced phytotoxicity being due to (−)-botryodiplodin, not phaseolinone or other unknown impurities. Soybean leaf disc cultures of Saline cultivar were more susceptible to (±)-botryodiplodin phytotoxicity than were cultures of two charcoal rot-resistant genotypes, DS97-84-1 and DT97-4290. (±)-Botryodiplodin caused similar phytotoxicity in actively growing duckweed (Lemna pausicostata) plantlet cultures, but at much lower concentrations. In soybean seedlings growing in hydroponic culture, (±)-botryodiplodin added to culture medium inhibited lateral and tap root growth, and caused loss of root caps and normal root tip cellular structure. Thus, botryodiplodin applied externally to undisturbed soybean roots induced phytotoxic responses of types expected to facilitate fungal root infection.

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Section: Preparation Of (±)-Botryodiplodinsupporting

confidence: 81%

Phytotoxic Responses of Soybean (Glycine max L.) to Botryodiplodin, a Toxin Produced by the Charcoal Rot Disease Fungus, Macrophomina phaseolina

Abbas

Bellaloui

Butler

et al. 2020

Toxins

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“…(3 R ,4 S )-(-)-Botryodiplodin ( 42 ) was the first compound, belonging to this series, isolated from a liquid culture of a ligninolytic strain of L. theobromae , and reported by [ 24 ] as a new antibiotic product, but its structure and stereostructure were subsequently determined [ 75 , 76 , 77 , 78 ]. Moreover, (±)-botryodiplodin and its stereoisomers were also prepared through numerous synthetic procedures [ 79 ]. (3 R ,4 S )-(-)-Botryodiplodin was also isolated as a product of other fungal species, such as L. mediterranea [ 73 ] and M. phaseolina [ 80 ].…”

Section: Secondary Metabolitesmentioning

confidence: 99%

Secondary Metabolites of Lasiodiplodia theobromae: Distribution, Chemical Diversity, Bioactivity, and Implications of Their Occurrence

Salvatore

Alves

Andolfi

2020

Toxins

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Lasiodiplodia theobromae is a plant pathogenic fungus from the family Botryosphaeriaceae that is commonly found in tropical and subtropical regions. It has been associated with many hosts, causing diverse diseases and being responsible for serious damages on economically important crops. A diverse array of bioactive low molecular weight compounds has been described as being produced by L. theobromae cultures. In this review, the existing literature on secondary metabolites of L. theobromae, their bioactivity, and the implications of their occurrence are compiled. Moreover, the effects of abiotic factors (e.g., temperature, nutrient availability) on secondary metabolites production are highlighted, and possible avenues for future research are presented. Currently, a total of 134 chemically defined compounds belonging to the classes of secondary metabolites and fatty acids have been reported from over 30 L. theobromae isolates. Compounds reported include cyclohexenes and cyclohexenones, indoles, jasmonates, lactones, melleins, phenols, and others. Most of the existing bioactivity studies of L. theobromae metabolites have assessed their potential phytotoxic, cytotoxic, and antimicrobial activities. In fact, its host adaptability and its ability to cause diseases in plants as well as in humans may be related to the capacity to produce bioactive compounds directly involved in host–fungus interactions.

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“…[183] The asymmetric synthesis of (À)-botryodiplodin was accomplished by Nouguier et al by using the radical cyclization of an allenyl bromoacetal as the key step (Scheme 68). [184] The configuration of the resulting 4-vinyl-substituted tetrahydrofuran was controlled by the stereogenic acetal center, where (1R,2S)-2-phenylcyclohexanol was applied as a chiral auxiliary. Stereoselective reduction followed by a Wacker oxidation to convert the vinyl moiety into an acetyl group led to (À)-botryodiplodin.…”

Section: Radical Cyclizationsmentioning

confidence: 99%

Allenes in Catalytic Asymmetric Synthesis and Natural Product Syntheses

2012

Angew Chem Int Ed

963

259

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Allenes are the simplest class of cumulenes, with two contiguous C=C bonds, and show unique physical and chemical properties. These features make allenes particularly attractive in modern organic chemistry. In this Review, attention is paid to the advances made in catalytic asymmetric synthesis and natural product syntheses based on well-established reactions of allenes, such as propargylation, addition, cycloaddition, cycloisomerization, cyclization, etc., with or without catalysts. Their versatile reactivity, substituent-loading ability, axial to center chirality transfer, and controllable selectivity allow access to target molecules by unique and efficient approaches. The main topics in this Review are presented with selected examples from 2003 to 2011.

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Synthesis of (±)- and (−)-botryodiplodin using stereoselective radical cyclizations of acyclic esters and acetals

Cited by 32 publications

References 53 publications

Phytotoxic Responses of Soybean (Glycine max L.) to Botryodiplodin, a Toxin Produced by the Charcoal Rot Disease Fungus, Macrophomina phaseolina

Phytotoxic Responses of Soybean (Glycine max L.) to Botryodiplodin, a Toxin Produced by the Charcoal Rot Disease Fungus, Macrophomina phaseolina

Secondary Metabolites of Lasiodiplodia theobromae: Distribution, Chemical Diversity, Bioactivity, and Implications of Their Occurrence

Allenes in Catalytic Asymmetric Synthesis and Natural Product Syntheses

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