Synthesis of Osthole Derivatives with Grignard Reagents and Their Larvicidal Activities on Mosquitoes

Liu, Ming; Liu, Yang; Hua, Xuewen; Wu, Changchun; Zhou, Sha; Wang, Baolei; Li, Zhengming

doi:10.1002/cjoc.201500620

Cited by 17 publications

(12 citation statements)

References 46 publications

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“…The 8-iodocoumarin derivative underwent a Stille crosscoupling reaction with tributyl (3-methylbut-2-en-1-yl) stannane in the presence of a catalytic amount of Pd (PPh 3 ) 4 in DMF at 80°C, resulting in productive yields of osthole [21]. Similarly, an inexpensive and eco-friendly method to synthesize osthole with a Grignard reagent assisted by non-precious metals was developed by Liu et al This method employed CuI and LiCl as promoters and covered 7-methoxyl-8-iodocoumarin (7) to result in osthole with a yield of 80% (Scheme 2) [22].…”

Section: Synthesismentioning

confidence: 99%

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Osthole: an overview of its sources, biological activities, and modification development

Sun

Zhang

2021

Med Chem Res

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Osthole, also known as osthol, is a coumarin derivative found in several medicinal plants such as Cnidium monnieri and Angelica pubescens. It can be obtained via extraction and separation from plants or total synthesis. Plenty of experiments have suggested that osthole exhibited multiple biological activities covering antitumor, anti-inflammatory, neuroprotective, osteogenic, cardiovascular protective, antimicrobial, and antiparasitic activities. In addition, there has been some research done on the optimization and modification of osthole. This article summarizes the comprehensive information regarding the sources and modification progress of osthole. It also introduces the up-to-date biological activities of osthole, which could be of great value for its use in future research.

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Section: Synthesismentioning

confidence: 99%

“…Liu et al developed an efficient method using Grignard reagents to synthesize osthole derivatives and evaluated their larvicidal activities on mosquitoes [22]. Synthesis of compounds 86 were similar to that of osthole described above.…”

Section: Analogs Modified With Multiple Sites Of Coumarinmentioning

confidence: 99%

Osthole: an overview of its sources, biological activities, and modification development

Sun

Zhang

2021

Med Chem Res

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“…Following the general procedure, 3e (220 mg, 1.00 mmol) was converted to 7e (176 mg, 0.72 mmol, 72%): orange-colored solid, mp 80−83 °C; 1 H NMR (300 MHz, CDCl 3 ) δ 7.63 (d, J = 9.5 Hz, 1H), 6.97 (d, J = 2.9 Hz, 1H), 6.73 (d, J = 2.9 Hz, 1H), 6.39 (d, J = 9.5 Hz, 1H), 5.31 (tm, J = 7.4 Hz, 1H), 3.81 (s, 3H), 3.51 (d, J = 7.4 Hz, 2H), 1.74 (s, 3H), 1.73 (s, 3H); 13 7-Methoxy-8-(3-methylbut-2-en-1-yl)-4-phenyl-2H-chromen-2one (7f). 89 Following the general procedure, 3f (296 mg, 1.00 mmol) was converted to 7f (291 mg, 0.91 mmol, 91%): orange-colored solid, mp 110−112 °C; 1 H NMR (300 MHz, acetone-d 6 ) δ 7.61−7.48 (m, 5H), 7.29 (d, J = 8.9, 1H), 6.99 (d, J = 8.9, 1H), 6.12 (s, 1H), 5.24 (t, J = 7.0, 1H), 3.95 (s, 3H), 3.54 (d, J = 7.0, 2H), 1.85 (s, 3H), 1.66 (s, 3H); 13 6-Methoxy-4-methyl-8-(3-methylbut-2-en-1-yl)-2H-chromen-2one (7i). Following the general procedure, 3i (234 mg, 1.00 mmol) was converted to 7i (216 mg, 0.84 mmol, 84%): yellowish oil; 1 H NMR (300 MHz, CDCl 3 ) δ 6.97 (d, J = 2.9 Hz, 1H), 6.84 (d, J = 2.9 Hz, 1H), 6.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Prenylcoumarins in One or Two Steps by a Microwave-Promoted Tandem Claisen Rearrangement/Wittig Olefination/Cyclization Sequence

Schultze

Schmidt

2018

J. Org. Chem.

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The one-pot synthesis of 8-prenylcoumarins from 1,1-dimethylallylated salicylaldehydes and the stabilized ylide [(ethoxycarbonyl)methylene]triphenylphosphorane under microwave conditions was found to have a limited scope. The sequence suffers from a difficult and sometimes low-yielding synthesis of the precursors and from a competing deprenylation upon microwave irradiation. This side reaction occurs in particular with electron rich arenes with two or more alkoxy groups at adjacent positions, a prominent substitution pattern in naturally occurring 8-prenylcoumarins. Both limitations of this one-step sequence were overcome by a two-step synthesis consisting of a microwave-promoted tandem allyl ether Claisen rearrangement/Wittig olefination and a subsequent olefin cross metathesis with 2-methyl-2-butene. The cross metathesis step proceeds with a high selectivity and yields exclusively the desired prenyl, rather than the alternative crotyl substituent. Several naturally occurring 8-prenylcoumarins that were previously inaccessible have been synthesized in good overall yields along this route.

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“…1) is a coumarin-like compound isolated from the Chinese medicine Cnidium monnieri and has obvious significant medical activities including anti-inflammation, 6,7 anti-osteoporosis, 8,9 hepatoprotection, 10,11 antitumor, [12][13][14] anti-Alzheimer's disease, 15,16 antibacteria 17 and anti-hyperlipidemia. 18 In addition, as osthole is less risky for human health and the environment, 19 it has been used as antifungal, larvicidal and anthelminthic agents against plant pathogenic fungi, 20 mosquitoes 21,22 and Dactylogyrus intermedius, 23 respectively. However, its agricultural activities are far from being comparable to traditional agrochemicals.…”

Section: Introductionmentioning

confidence: 99%

Construction of oxime ester derivatives of osthole from Cnidium monnieri, and evaluation of their agricultural activities and control efficiency

Ren¹,

et al. 2020

Pest Management Science

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BACKGROUND: In order to discover natural-product-based pesticidal candidates, a series of coumarin-like derivatives containing oxime ester fragments at the C-8 position were prepared by structural modification of osthole, a natural plant product isolated from Cnidium monnieri. Their pesticidal activities were evaluated against two typically fruit trees/crop-threatening agricultural pests, Mythimna separata Walker and Tetranychus cinnabarinus Boisduval. RESULTS: Osthole was regioselectively oxidized by selenium dioxide to give the E-isomer, (2 0 E)-3 0-formaldehydylosthole (2). Four key steric structures of 2, (2'E, 4'E)-(o-chloropyrid-3-ylcarbonyl)oximinylosthole (4o), (2'E, 4'E)-(styrylcarbonyl)oximinylosthole (4t), and (2'E, 4'E)-(acetyl)oximinylosthole (4w) were undoubtedly confirmed by X-ray crystallography. Against T. cinnabarinus, it is noteworthy that (2 0 E, 4 0 E)-(p-chlorophenylcarbonyl)oximinylosthole (4c) exhibited over threefold more potent acaricidal activity of the precursor osthole, with especially good control efficiency observed in the glasshouse. Against M. separata, compounds 4c and (2 0 E, 4 0 E)-(p-nitrophenylcarbonyl)oximinylosthole (4f) showed the most pronounced growth inhibitory activity. The relationships between their structures and agricultural activities also were studied. CONCLUSION: These results demonstrate that compound 4c could be further structurally modified as pesticidal agents. It will lay the foundation for future application of osthole derivatives as pesticides.

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Synthesis of Osthole Derivatives with Grignard Reagents and Their Larvicidal Activities on Mosquitoes

Cited by 17 publications

References 46 publications

Osthole: an overview of its sources, biological activities, and modification development

Osthole: an overview of its sources, biological activities, and modification development

Prenylcoumarins in One or Two Steps by a Microwave-Promoted Tandem Claisen Rearrangement/Wittig Olefination/Cyclization Sequence

Construction of oxime ester derivatives of osthole from Cnidium monnieri, and evaluation of their agricultural activities and control efficiency

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