Shimalactone Biosynthesis Involves Spontaneous Double Bicyclo‐Ring Formation with 8π‐6π Electrocyclization

Fujii, Isao; Hashimoto, Makoto; Konishi, Kimiko; Unezawa, Akiko; Sakuraba, Haruka; Suzuki, Kenta; Tsushima, Harue; Iwasaki, Masa; Yoshida, Satsuki; Kudo, Akane; Fujita, Rina; Hichiwa, Aika; Saito, Koharu; Asano, Takashi; Ishikawa, Jun; Wakana, Daigo; Goda, Yukihiro; Watanabe, Akiteru; Watanabe, Mamoru; Masumoto, Yui; Kanazawa, Junichiro; Sato, Hajime; Uchiyama, Masanobu

doi:10.1002/anie.202001024

Cited by 23 publications

(15 citation statements)

References 43 publications

(23 reference statements)

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“…311 The BGC responsible for biosynthesis of the neuritogenic polyketides, shimalactones, was identified and the complete biosynthetic route for these metabolites elucidated via experimental and computational studies. 312 The BGC responsible for biosynthesis of the alkaloid brevianamide A in Penicillium brevicompactum has been identified and the pathway determined. 313 Formation of crustosic acid in Penicillium crustosum was investigated by gene deletion and heterologous expression.…”

Section: Marine Microorganisms and Phytoplanktonmentioning

confidence: 99%

Marine natural products

et al. 2022

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Section: Marine Microorganisms and Phytoplanktonmentioning

confidence: 99%

Marine natural products

et al. 2022

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“…With the identification of the ast gene cluster, heterologous reconstitution of biosynthetic pathways was further performed in S. cerevisiae BJ5464-NpgA to probe the unique SPase referred to previous studies. ,− Combinatory heterologous expression of astA , astA/B , and astA/B/C in yeast produced the same metabolites as an expression of aurA , aurA/B , and aurA/B/C , respectively (Figure S12), suggesting that neither AstB nor AstC was the SPase. However, when astD was additionally expressed in S.…”

Section: Resultsmentioning

confidence: 92%

Discovery of Semi-Pinacolases from the Epoxide Hydrolase Family during Efficient Assembly of a Fungal Polyketide

et al. 2021

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The semipinacol rearrangement (SPR) is highly useful in the asymmetric synthesis of complex compounds. In biological systems, only a few semi-pinacolases belonging to a few families have been identified to catalyze the SPR on alkaloids. Here, based on the biosynthesis of a fungal mycotoxin asteltoxin (1), two semi-pinacolases AstD/MrvD were identified from the epoxide hydrolase family to catalyze type III SPR on the polyketide backbone. They were proposed to catalyze efficient regio-selective hydrolysis on the bis-epoxide and 2,3-migration on the epoxide alcohol for the rearrangement. Based on the comprehensive mutations and chemical calculations, a critical Asp residue was identified as an acid for the coupled catalysis of selective epoxide collapse and subsequent SPR, while other critical residues facilitated efficient hydrolysis and protected carbocation for SPR. Thus, this study expanded the SPR biocatalyst family and provided an understanding of the catalytic mechanisms of these bifunctional semi-pinacolases.

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“…The relative free energies are presented in Figure in kilojoules per mole. Computational studies on the 8π/6π electrocyclic cascades of linear tetraenes have been reported by Houk, Uchiyama, Cossío, and our own laboratory …”

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confidence: 71%

“…The relative free energies are presented in Figure 3 in kilojoules per mole. Computational studies on the 8π/6π electrocyclic cascades of linear tetraenes have been reported by Houk, 25 Uchiyama, 26 Cossi ́o, 27 and our own laboratory. 12 The 1,5-addition/ring opening of 1 with a methyl nucleophile would lead to cyclooctatriene-enolate 14 (a truncated model system).…”

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confidence: 80%

Two Steps to Bicyclo[4.2.0]octadienes from Cyclooctatetraene: Total Synthesis of Kingianic Acid A

Patel

Fallon

2022

Org. Lett.

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Synthetic approaches to bicyclo[4.2.0]octadiene natural products frequently employ the synthesis of linear tetraenes to initiate a biosynthetic 8π/6πelectrocyclization cascade. This work forges a functionalized bicyclo[4.2.0]octadiene in two steps from cyclooctatetraene. The versatility of this method is demonstrated through natural product synthesis, including the first total synthesis of kingianic acid A and formal syntheses of kingianins A, D, and F and cryptobeilic acid D ethyl ester. The unexpected formation of an E,E,Z,E-tetraene byproduct is rationalized through density functional theory modeling.

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Shimalactone Biosynthesis Involves Spontaneous Double Bicyclo‐Ring Formation with 8π‐6π Electrocyclization

Abstract: Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Cited by 23 publications

References 43 publications

Marine natural products

Marine natural products

Discovery of Semi-Pinacolases from the Epoxide Hydrolase Family during Efficient Assembly of a Fungal Polyketide

Two Steps to Bicyclo[4.2.0]octadienes from Cyclooctatetraene: Total Synthesis of Kingianic Acid A

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