Model Synthetic Study of Tutin, a Picrotoxane-Type Sesquiterpene: Stereoselective Construction of a &lt;i&gt;cis&lt;/i&gt;-Fused 5,6-Ring Skeleton

Ikeuchi, Kazutada; Haraguchi, Shota; Yamada, Hidetoshi; Tanino, Keiji

doi:10.1248/cpb.c22-00083

Cited by 4 publications

(2 citation statements)

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“…We recently reported a method for the desymmetrization of a 1,3-cyclopentanedione moiety via the intramolecular aldol reaction of rac -aldehyde 9 with dl -proline (Scheme a). , This reaction involves the formation of an intramolecular hydrogen bond between a carbonyl group in the 1,3-cyclopentanedione and the carboxylic group of enamine intermediate 10 , derived from ( R )- 9 and l -proline, or ( S )- 9 and d -proline (not shown in Scheme a), to afford bicyclic compound 11 in 73% yield along with a trace amount of its diastereomer, 12 . The stereochemistries of the two contiguous angular centers in 12 correspond to those in 3 , which inspired us to develop this methodology for the total synthesis of 3 .…”

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Total Synthesis of (+)-Coriamyrtin via a Desymmetrizing Strategy Involving a 1,3-Cyclopentanedione Moiety

et al. 2023

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We describe the total synthesis of (+)-coriamyrtin, which bears a highly functionalized cis-hydrindane skeleton and is a widely known neurotoxin of the Coriariaceae family. Our synthetic strategy involves the highly stereoselective construction of the cishydrindane skeleton via a desymmetrizing strategy involving a 1,3cyclopentanedione moiety using an intramolecular aldol reaction and the formation of the 1,3-diepoxide moiety of coriamyrtin through the elaborate functionalization of the cyclopentane ring in the bicyclic structure. P icrotoxane-type sesquiterpenes are widely distributed in plants, such as Coriariaceae, Orchidaceae, and Menispermaceae. 1 Since picrotoxin, which is a poisonous compound composed of a 1:1 mixture of picrotoxinin (1) and picrotin (2), was found in Menispermum cocculus in 1818, more than 130 picrotoxane-type natural products have been isolated (Figure 1). 2 Because 1 is a strong antagonist of the γ-

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Total Synthesis of (+)-Coriamyrtin via a Desymmetrizing Strategy Involving a 1,3-Cyclopentanedione Moiety

et al. 2023

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“…We recently reported a method for the desymmetrization of a 1,3-cyclopentadione moiety via the intramolecular aldol reaction of rac-aldehyde 3 with DL-proline (Scheme 1a). [14] This reaction involves an intramolecular hydrogen bond formation between a carbonyl group in the 1,3-cyclopentanedione and the carboxylic group of enamine intermediate 4, derived from (R)-3 and L-proline, or (S)-3 and D-proline (not be shown in Scheme 1a), to afford the bicyclic compound 5 in 73% yield along with a trace amount of its diastereomer 6. The two contiguous centers of the angular The retrosynthesis of coriamyrtin (2) is shown in Scheme 1b.…”

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Total Synthesis of (+)-Coriamyrtin via a Desymmetric Strategy of a 1,3-Cyclopentanedione Moiety

Ikeuchi

Haraguchi

Fujii

et al. 2022

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This paper describes the total synthesis of (+)-coriamyrtin, a picrotoxane-type sesquiterpene. The natural product is widely known as a neurotoxin of the Coriariaceae family and bears a highly functionalized cis-hydrindane skeleton. Despite being biologically and synthetically attractive molecule, only two examples of the total synthesis are reported to date. Our synthetic strategy involves the highly stereoselective construction of the cis-hydrindane skeleton via the desymmetric strategy of a 1,3-cyclopentanedione moiety using an intramolecular aldol reaction and elaborate functionalization of the cyclopentane ring in the bicyclic structure for the formation of the 1,3-diepoxide moiety of coriamyrtin. Our method could be applied to synthesize various natural products with similar bicyclic skeletons and to expand neurobiological studies using synthesized products.

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Synthesis of 2-Alkyl-2-(2-furanyl)-1,3-cyclopentanediones

et al. 2022

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2,2-Disubstituted-1,3-cyclopentanediones are versatile building blocks for synthesizing complex natural products with bicyclic structures including cyclopentane rings. The reported method for the synthesis of these compounds involves the semi-pinacol rearrangement of a Mukaiyama-aldol adduct prepared from a ketone/ketal and 1,2-bis(trimethylsilyloxy)cyclobutene. However, the adoption of α-oxy-functionalized ketones/ketals is quite difficult, as demonstrated by our experiments. To overcome this limitation of the method, we used 2-acylfuran derivatives as the reactants to synthesize 2,2-disubstituted-1,3-cyclopentanediones. Furthermore, two reaction conditions, that is, the use of 1.4 equivalents of a boron trifluoride-diethyl ether complex or 0.4 and 0.2 equivalents of trimethylsilyl triflate and methoxytrimethylsilane, respectively, were established for the conversion of 2-acylfurans into the corresponding 1,3-cyclopentanediones in acceptable yields. The transformations of the furan rings in the obtained products were also investigated.

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Model Synthetic Study of Tutin, a Picrotoxane-Type Sesquiterpene: Stereoselective Construction of a <i>cis</i>-Fused 5,6-Ring Skeleton

Cited by 4 publications

References 32 publications

Total Synthesis of (+)-Coriamyrtin via a Desymmetrizing Strategy Involving a 1,3-Cyclopentanedione Moiety

Total Synthesis of (+)-Coriamyrtin via a Desymmetrizing Strategy Involving a 1,3-Cyclopentanedione Moiety

Total Synthesis of (+)-Coriamyrtin via a Desymmetric Strategy of a 1,3-Cyclopentanedione Moiety

Synthesis of 2-Alkyl-2-(2-furanyl)-1,3-cyclopentanediones

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