Total Synthesis and Structure Confirmation of <i>trans</i>-Anhydromevalonate-5-phosphate, a Key Biosynthetic Intermediate of the Archaeal Mevalonate Pathway

Yasuno, Yoko; Nakayama, Atsushi; Saito, Kai; Kitsuwa, Kohei; Okamura, Hajime; Komeyama, Mutsumi; Hemmi, Hisashi; Shinada, Tetsuro

doi:10.1021/acs.jnatprod.1c00615

Cited by 5 publications

(20 citation statements)

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“…Starting from 20, the first total synthesis of tAHMP (2) was achieved (Scheme 1C). 9 We envisioned that tAHM group-containing natural products 1 and 3−8 could be prepared from tAHMA methyl ester (20) and tAHMA tert-butyl ester (27). Esters 20 and 27 would be properly selected as a starting material in consideration of the molecular and functional group complexity of the target natural products, to achieve our goal.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…tAHMA (1). Procedure A: To a solution of tAHMA methyl ester (20) 9 (100 mg, 0.694 mmol) in THF/H 2 O (6.0 mL, 2:1 v/v) was added LiOH•H 2 O (64.1 mg, 1.53 mmol) at 0 °C. The mixture was stirred for 16 h at room temperature (rt), quenched with 1 M aqueous HCl, and concentrated under reduced pressure.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Procedure B: To a solution of tAHMA methyl ester (20) 9 (50.0 mg, 0.347 mmol) in dichloroethane (DCE) (3.0 mL) was added Me 3 SnOH (62.7 mg, 0.347 mmol) at rt. After stirring for 1.5 h at 60 °C, additional Me 3 SnOH (total 690 mg, 3.82 mmol, four portions) was added to the solution and the mixture was stirred for 66.5 h at 80 °C.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Recently, we have reported a stereoselective synthesis of tAHMA methyl ester 20 and its application to the first total synthesis of tAHMP (2) (Scheme 1C). 9 In our continuing research program toward the development of stereoselective syntheses of tAHM group-containing natural products, we planned syntheses of tAHMA (1), pestalotiopin A (3), farinomalein E (4), pestalotiopamide C (5), pestalotiopamide D (6), eleutherazine B (7), and trichocyclodipeptide A (8). In this paper, we would like to report a stereoselective synthesis of tAHMA tert-butyl ester 27 and total syntheses of 1,3,4,5,6,7, and 8 from esters 20 and 27.…”

mentioning

confidence: 99%

“…Pestalotiopin A Methyl Ester (21). To a solution of tAHMA methyl ester (20)9 (50.0 mg, 0.347 mmol) in pyridine (0.52 mL) were…”

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confidence: 99%

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Stereoselective Syntheses of trans-Anhydromevalonic Acid and trans-Anhydromevalonyl Group-Containing Natural Products

et al. 2022

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Collective total syntheses of trans-anhydromevalonic acid (tAHMA) and trans-anhydromevalonyl (tAHM) groupcontaining natural products (pestalotiopin A, pestalotiopamide C, pestalotiopamide D, farinomalein E, eleutherazine B, and trichocyclodipeptide A) were achieved using tAHMA esters as key intermediates. To this end, tAHMA tert-butyl ester was newly prepared by Z-vinyltosylation of tert-butyl 3-oxo-5-((triisopropylsilyl)oxy)pentanoate followed by the Negishi cross-coupling reaction with Me 2 Zn. tAHMA esters were converted to the target natural products via esterification or amidation. Comparison of the spectroscopic data of synthetic and natural products confirmed the E-configuration of the tAHM moieties in the natural products.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

mentioning

confidence: 99%

“…Pestalotiopin A Methyl Ester (21). To a solution of tAHMA methyl ester (20)9 (50.0 mg, 0.347 mmol) in pyridine (0.52 mL) were…”

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confidence: 99%

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Stereoselective Syntheses of trans-Anhydromevalonic Acid and trans-Anhydromevalonyl Group-Containing Natural Products

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Quinquevalent phosphorus acids

Bałczewski,

Owsianik

2024

Organophosphorus Chemistry

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This chapter shows, as in previous years, the most important achievements of the 2021 year in the area of organo-phosphorus compounds containing: three P–O bonds (Section 2: phosphoric acids and their derivatives), two P–O and one P–C bonds (Section 3: phosphonic acids and their derivatives) as well as one P–O and two P–C bonds (Section 4: phosphinic acids and their derivatives), in addition to the phosphoryl group P═O, present in all three groups of compounds. Each of the main sections covers “synthesis and reactions” including pure synthesis without applications, “synthesis and biological applications” and “synthesis and miscellaneous applications” including synthesis directed towards non-biological applications. At the end of each subsection, the corresponding achievements are shown for hetero-analogues in which phosphorus–oxygen bonds have been replaced by phosphorus–heteroatom P–X and/or P═Y bonds (X, Y = N, S or Se). The subsection on quinquevalent phosphorus acids and their derivatives as catalysts has been placed, as usual, at the end of the entire chapter, after a review of all three main groups of compounds. As in previous years, the area devoted to phosphoric and phosphonic acids and their derivatives dominated over a smaller section of phosphinic acids and their derivatives, and literature references for these sections remained at a ratio of 4 : 12 : 1. A dynamic, five-fold increase in the number of works, in the subject of chiral phosphoric acids as catalysts, has been recorded in this year.

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Archaeal mevalonate pathway in the uncultured bacterium Candidatus Promineifilum breve belonging to the phylum Chloroflexota

Kanno,

Kuriki,

Yasuno

et al. 2024

Appl Environ Microbiol

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The archaeal mevalonate pathway is a recently discovered modified version of the eukaryotic mevalonate pathway. This pathway is widely conserved in archaea, except for some archaeal lineages possessing the eukaryotic or other modified mevalonate pathways. Although the pathway seems almost exclusive to the domain Archaea, the whole set of homologous genes of the pathway is found in the metagenome-assembled genome sequence of an uncultivated bacterium, Candidatus Promineifilum breve, of the phylum Chloroflexota. To prove the existence of the archaea-specific pathway in the domain Bacteria, we confirmed the activities of the enzymes specific to the pathway, phosphomevalonate dehydratase and anhydromevalonate phosphate decarboxylase, because only these two enzymes are absent in closely related Chloroflexota bacteria that possess a different type of modified mevalonate pathway. The activity of anhydromevalonate phosphate decarboxylase was evaluated by carotenoid production via the archaeal mevalonate pathway reconstituted in Escherichia coli cells, whereas that of phosphomevalonate dehydratase was confirmed by an in vitro assay using the recombinant enzyme after purification and iron-sulfur cluster reconstruction. Phylogenetic analyses of some mevalonate pathway-related enzymes suggest an evolutionary route for the archaeal mevalonate pathway in Candidatus P. breve, which probably involves horizontal gene transfer events. IMPORTANCE The recent discovery of various modified mevalonate pathways in microorganisms, such as archaea and Chloroflexota bacteria, has shed light on the complexity of the evolution of metabolic pathways, including those involved in primary metabolism. The fact that the archaeal mevalonate pathway, which is almost exclusive to the domain Archaea, exists in a Chloroflexota bacterium provides valuable insights into the molecular evolution of the mevalonate pathways and associated enzymes. Putative genes probably involved in the archaeal mevalonate pathway have also been found in the metagenome-assembled genomes of Chloroflexota bacteria. Such genes can contribute to metabolic engineering for the bioproduction of valuable isoprenoids because the archaeal mevalonate pathway is known to be an energy-saving metabolic pathway that consumes less ATP than other mevalonate pathways do.

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Total Synthesis and Structure Confirmation of trans-Anhydromevalonate-5-phosphate, a Key Biosynthetic Intermediate of the Archaeal Mevalonate Pathway

Cited by 5 publications

References 12 publications

Stereoselective Syntheses of trans-Anhydromevalonic Acid and trans-Anhydromevalonyl Group-Containing Natural Products

Stereoselective Syntheses of trans-Anhydromevalonic Acid and trans-Anhydromevalonyl Group-Containing Natural Products

Quinquevalent phosphorus acids

Archaeal mevalonate pathway in the uncultured bacterium Candidatus Promineifilum breve belonging to the phylum Chloroflexota

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