Asymmetric Total Synthesis of <i>ent</i>‐Pyripyropene A

Fuse, Shinichiro; Ikebe, Ayako; Oosumi, Kazuya; Karasawa, Tomoya; Matsumura, Keisuke; Izumikawa, Miho; Johmoto, Kohei; Uekusa, Hidehiro; Shin‐ya, Kazuo; Doi, Takayuki; Takahashi, Takashi

doi:10.1002/chem.201500703

Cited by 16 publications

(10 citation statements)

References 62 publications

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“…However, the Katritzky group had reported a one-step conversion of 7 to 10 using 1-acylbenzotriazoles, and LDA as base [ 69 , 70 ]. Although the reported yields were only modest for simple aliphatic 1-acylbenzotriazoles (ca.…”

Section: Resultsmentioning

confidence: 99%

Novel, male-produced aggregation pheromone of the cerambycid beetle Rosalia alpina, a priority species of European conservation concern

et al. 2017

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Several recent studies have demonstrated the great potential for exploiting semiochemicals in ecology and conservation studies. The cerambycid beetle Rosalia alpina represents one of the flagship species of saproxylic insect biodiversity in Europe. In recent years its populations appear to have declined substantially, and its range has shrunk considerably as a result of forest management and urbanization. Here, we collected volatile chemicals released by males and females of R. alpina. Analyses of the resulting extracts revealed the presence of a single male-specific compound, identified as a novel alkylated pyrone structure. In field bioassays in Slovenia, traps baited with the synthesized pyrone captured both sexes of R. alpina, indicating that the pyrone functions as an aggregation pheromone. Our results represent the first example of a new structural class of pheromones within the Cerambycidae, and demonstrate that pheromone-baited traps can provide a useful tool for sampling R. alpina. This tool could be particularly useful in the ongoing development of conservation strategies for the iconic but endangered Alpine longicorn.

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Section: Resultsmentioning

confidence: 99%

Novel, male-produced aggregation pheromone of the cerambycid beetle Rosalia alpina, a priority species of European conservation concern

et al. 2017

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“…[e] MYZUPE Myzus persicae green peach aphid. [f] We previously reported ED 50 (The concentration corresponding to 50% mortality) of pyripyropene A against MYZUPE (8 ppm) …”

Section: Resultsmentioning

confidence: 99%

“…Therefore, we envisaged that the substituents R 1 -R 3 could be sequentially introduced in the order indicatedi nS cheme 1. In our total synthesis of pyripyropene A, [8] introduction of the 3-pyridyl group decreasedt he solubility of the compound against various organic solvents. Therefore, we planned to introduce the 3-pyridyl group in the final step.…”

Section: Resultsmentioning

confidence: 99%

“…[7] We recently reported the convergent synthesis of ent-pyripyropene Ab ased on our originally developed tandem radical cyclizationu sing ac atalytic amount of aT i III reagent. [8] Although the total synthesis of pyripyropene Aw as accomplished, many synthetic steps (more than 15) were required. For further development of pyripyropene-based agrichemicals, the developmento fm ore synthetically accessible templates [9] that retain an insecticidals pectrum similar to that of pyripyropeneA is an important starting point.…”

Section: Introductionmentioning

confidence: 95%

“…Ōmura, Smith and co‐workers achieved the first total synthesis of pyripyropene A in a highly convergent manner, and Ōmura, Nagamitsu and colleagues more recently developed a practical, linear synthetic route for the total synthesis of pyripyropene A . We recently reported the convergent synthesis of ent ‐pyripyropene A based on our originally developed tandem radical cyclization using a catalytic amount of a Ti III reagent . Although the total synthesis of pyripyropene A was accomplished, many synthetic steps (more than 15) were required.…”

Section: Introductionmentioning

confidence: 99%

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The Design, Synthesis, and Evaluation of 1,5,7‐Trisubstituted‐3‐Pyridyl‐Xanthones for Use as Insecticides Starting from Pyripyropene A

Fuse

Matsumura

Johmoto

et al. 2016

Chemistry A European J

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A readily accessible template of 1,5,7-trisubstituted-3-pyridyl-xanthones was designed starting from naturally occurring pyripyropene A for agrichemical development. Our originally developed Ag CO -mediated oxidative cyclization enabled ready access to the key scaffold, 1,5,7-trihydroxy-3-chloro-xanthone. The chemo- and regioselective sequential introduction of four substituents to the scaffold rapidly afforded the desired, structurally diverse 1,5,7-trisubstituted-3-pyridyl-xanthones. An evaluation of insecticidal activity revealed that one of the synthesized compounds retained insecticidal activity against vetch aphid and green peach aphid. The observed insecticidal spectrum was similar to that of pyripyropene A. The developed template could be a valuable aid for future agrichemical development.

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Ring‐Opening Reactions of Epoxides With Titanium(III) Reagents

RajanBabu¹,

Nugent²,

Halder³

2022

Organic Reactions

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The ring‐opening reactions of epoxides with titanium(III) reagents such as Cp 2 TiCl are critically reviewed, including the scope, limitations, and mechanism of these synthetically useful transformations. The initial reaction proceeds by single‐electron transfer to give a carbon‐centered β‐titanoxy radical. The resulting radical can be terminated by a number of different reaction pathways, including epoxide deoxygenation, reduction to the alcohol, intermolecular addition to activated olefins, and intramolecular addition (cyclization). The literature is surveyed from the first reported examples in 1988 through October, 2021.

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Asymmetric Total Synthesis of ent‐Pyripyropene A

Cited by 16 publications

References 62 publications

Novel, male-produced aggregation pheromone of the cerambycid beetle Rosalia alpina, a priority species of European conservation concern

Novel, male-produced aggregation pheromone of the cerambycid beetle Rosalia alpina, a priority species of European conservation concern

The Design, Synthesis, and Evaluation of 1,5,7‐Trisubstituted‐3‐Pyridyl‐Xanthones for Use as Insecticides Starting from Pyripyropene A

Ring‐Opening Reactions of Epoxides With Titanium(III) Reagents

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