Synthesis and Determination of Absolute Configuration of Zealexin A1, a Sesquiterpenoid Phytoalexin from <i>Zea mays</i>

Yajima, Arata; Shimura, Mikaho; Saito, Tatsuo; Katsuta, Ryo; Huffaker, Alisa; Schmelz, Eric A.

doi:10.1002/ejoc.202001596

Cited by 4 publications

(1 citation statement)

References 29 publications

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“…As mentioned above, a detailed conformational search should first be performed (Mazzeo et al, 2014). Many known chiral compounds have been used this way in chiroptical spectroscopic study (Molteni et al, 2015;Stepanek and Bour, 2015;Pescitelli and Bruhn, 2016;Rossi et al, 2016;Johnson et al, 2018) while new synthetic chiral compounds have also been studied (Paolino et al, 2021;Yajima et al, 2021). Chiral compounds require one or two UV-vis chromophores in order to use ECD in their configuration assignments.…”

Section: Ecd and Its Usesmentioning

confidence: 99%

Computational methods and points for attention in absolute configuration determination

Zhu

Nafie

2023

Front. Nat. Prod.

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With the rapid development of high performance computers and computational methods, including software, an increasing number of experimental chemists have tried to use computational methods such as optical rotation (OR, including the matrix model), optical rotatory dispersion (ORD), electronic circular dichroism (ECD or CD), vibrational circular dichroism (VCD), and magnetic shielding constants—nuclear magnetic resonance (NMR)—to explain and/or assign absolute configuration (AC) for various compounds. Such reports in the field of natural products have increased dramatically. However, every method has its range of application. This leads, in some cases, to incorrect conclusions by researchers who are not familiar with these methods. In this review, we provide experimental chemists and researchers with more computational details and suitable suggestions, and especially hope that this experience may help readers avoid computational pitfalls. Finally, we discuss the use of simplified models to replace original complex structures with a long side chain. The fundamental basis for using models to represent complex chiral compounds, such as in OR calculations, is the existence of conformation pairs with near canceling conformer contributions that justify the use of models rather than the original compounds. Using examples, we here introduce the transition state (TS) calculation, which may benefit readers in this area for use and mastery for their AC study. This review will summarize the general concepts involved in the study of AC determinations.

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Section: Ecd and Its Usesmentioning

confidence: 99%

Computational methods and points for attention in absolute configuration determination

Zhu

Nafie

2023

Front. Nat. Prod.

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Comprehensive Engineering Strategies for Heterologous Production of Zealexin A1 in Saccharomyces cerevisiae

Li,

et al. 2024

J. Agric. Food Chem.

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Zealexin A1 is a nonvolatile sesquiterpene phytoalexin, which not only exhibits extensive antifungal and insecticidal activities but also has the ability to enhance the drought resistance of plants, and thus has potential applications in agricultural and food fields. In this study, the biosynthetic pathway of zealexin A1 was constructed in Saccharomyces cerevisiae for the first time, and the highest production of zealexin A1 reported to date was achieved. First, through screening of sesquiterpene synthases from various plants, BdMAS11 had a stronger (S)-β-macrocarpene synthesis ability was obtained, and the heterologous synthesis of zealexin A1 was achieved by coexpressing BdMAS11 with cytochrome P450 oxygenase ZmCYP71Z18. Subsequently, after the site-directed mutagenesis of BdMAS11, fusion expression of farnesyl diphosphate synthase ERG20 and BdMAS11, and tailored truncation of BdMAS11 and ZmCYP71Z18, the strain coexpressing the manipulated BdMAS11 and original ZmCYP71Z18 produced 119.31 mg/L of zealexin A1 in shake-flask fermentation. Finally, the production of zealexin A1 reached 1.17 g/L through fed-batch fermentation in a 5 L bioreactor, which was 261.7-fold that of the original strain. This study lays the foundation for the industrial production of zealexin A1 and other terpenoids.

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Engineering of Pichia pastoris for the De Novo Synthesis of the Sesquiterpene Zealexin A1 from Methanol

Niu,

Yan,

Wang

et al. 2024

ACS Sustainable Chem. Eng.

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Methanol is a promising one-carbon feedstock for the biomanufacturing of chemicals. In this study, we described the engineering of a Pichia pastoris strain capable of using methanol as a substrate to efficiently produce sesquiterpene phytoalexin zealexin A1. First, the cellular metabolism of P. pastoris was reconstructed to achieve high-level production of (S)-β-macrocarpene, the precursor of zealexin A1, by optimizing the MVA pathway, increasing the gene copy number of (S)-β-macrocarpene synthase, and downregulating the corresponding competitive pathway. The engineered strain produced 62.3 mg/L of (S)-β-macrocarpene. Second, cytochrome P450 enzyme (P450) CYP71Z18 was introduced to the strain to oxidize (S)-β-macrocarpene to zealexin A1, and 3.8 mg/L zealexin A1 was obtained from this approach. Finally, the supply of NADPH and methanol assimilation was enhanced to further improve the production of zealexin A1 by 24.8 mg/L. Subsequently, the engineered strain NT16 could produce 102.5 mg/L zealexin A1 under fed-batch fermentation carried out in a 5-L bioreactor. So far, this is the first time that zealexin A1 has been synthesized from methanol in P. pastoris.

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Synthesis and Determination of Absolute Configuration of Zealexin A1, a Sesquiterpenoid Phytoalexin from Zea mays

Cited by 4 publications

References 29 publications

Computational methods and points for attention in absolute configuration determination

Computational methods and points for attention in absolute configuration determination

Comprehensive Engineering Strategies for Heterologous Production of Zealexin A1 in Saccharomyces cerevisiae

Engineering of Pichia pastoris for the De Novo Synthesis of the Sesquiterpene Zealexin A1 from Methanol

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