Total synthesis of herbertenediol, an isocuparane sesquiterpene isolated from liverworts

Fukuyama, Yoshiyasu; Kiriyama, Yuuko; Kodama, Masashi

doi:10.1016/0040-4039(95)02411-5

Cited by 50 publications

(12 citation statements)

References 15 publications

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“…This chemical transformation confirmed the absolute configuration of jiadifenin. Another interesting majucin-subtype sesquiterpene, jiadifenolide (32), and jiadifenoxolanes A (33) and B (34), were isolated from the same plant [91]. Jiadifenolide (32) and jiadifenoxolane A (33) were found to significantly enhance the neurite outgrowth in primary cultured rat cortical neurons, in particular, jiadifenolide exhibited more potent activity at concentrations as low as 0.01 μM as shown in Fig.…”

Section: Neurotrophic Compounds From Illicium Speciesmentioning

confidence: 92%

“…However, the direct oxidation of herbertenediol (5) with (tert-BuO) 2 failed to yield dimers 1 and 2, resulting in a complex mixture, and thus protecting the 1-hydroxy group of 5 was essential for successful oxidative coupling. We applied horseradish peroxidase (HRP)-catalyzed oxidative phenolic coupling to 5, which resulted in the direct formation of 1 (10%) and 2 (18%) with recovery of 5 (72%) [32,33]. With a large amount of synthesized 1 and 2 in hand, the neurotrophic properties of 1 and 2 were evaluated in detail in primary cultured fetal rat cortical neurons.…”

Section: Mastigophora Dicladosmentioning

confidence: 99%

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The search for, and chemistry and mechanism of, neurotrophic natural products

Kubo

Harada

2020

J Nat Med

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Neurotrophic factors, now termed neurotrophins, which belong to a class of polypeptidyl agents, have been shown to potentially be beneficial for the treatment of neurodegenerative diseases such as Alzheimer's disease, because endogenous neurotrophic factors (NGF, BDNF, NT3, NT4) have been recognized to play critical roles in the promotion of neurogenesis, differentiation, and neuroprotection throughout the development of the central nervous system. However, high-molecular weight proteins are unable to cross the blood-brain barrier and are easily decomposed by peptidase under physiological conditions. To address this issue, small molecules that can mimic the functions of neurotrophic factors would be promising alternatives for the treatment of neurodegenerative disease. We have continued to search for natural products having typical neurotrophic properties, which can cause neurogenesis, enhance neurite outgrowth, and protect neuronal death using three cellular systems (PC12, rat cortical neurons, and MEB5 cells). In this review, we summarize the neurotrophic activities and synthesis of dimeric isocuparane-type sesquiterpenes from the liverwort, Mastigophora diclados, the mechanism of neurotrophic neolignans, magnolol, honokiol and their sesquiterpene derivatives, and introduce unique neurotrophin-mimic natural products, including seco-prezizaane-type sesquiterpenes from the Illicium species, vibsane-type diterpenes from Viburnum awabuki, and miscellaneous natural products with neurotrophic effects discovered by us.

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Section: Neurotrophic Compounds From Illicium Speciesmentioning

confidence: 92%

Section: Mastigophora Dicladosmentioning

confidence: 99%

The search for, and chemistry and mechanism of, neurotrophic natural products

Kubo

Harada

2020

J Nat Med

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“…Herbertenediol (1) is a sesquiterpene isolated from the liverworts Herberta adunca 18 and Radula perrottetii, 19 and has been subjected to biological studies, which showed potent anti-lipid peroxidation activity in rat brain homogenates (100% inhibition at 1 µg mL −1 ). 20 To date, seven asymmetric syntheses of herbertenediol have been reported, 21 with the shortest route reported by Abad and co-workers 21d comprising ten linear steps. Here the quaternary stereocenter was introduced by means of substrate control, as in the approach of Lin 21e and Kita et al 21f,g The Bringmann laboratory employed a kinetic resolution, 21b as did the Monti group, 21h to furnish enantiopure material.…”

Section: Resultsmentioning

confidence: 99%

Enantioselective palladium catalyzed conjugate additions of ortho-substituted arylboronic acids to β,β-disubstituted cyclic enones: total synthesis of herbertenediol, enokipodin A and enokipodin B

2014

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The palladium-catalyzed conjugate addition (Michael addition) of ortho-substituted arylboronic acids to β,β-disubstituted cyclic enones, in particular 3-methyl cyclopent-2-enone and 3-methyl cyclohex-2-enone, is reported. With an achiral bipyridine-based palladium catalyst, good yields are obtained with a variety of ortho-substituted arylboronic acids. In the asymmetric version, good to very high enantiomeric excesses (up to 99% ee) are obtained, though the yields are moderate. The decreased yields are attributed to significant protodeboronation of the arylboronic acid. The developed methodology allows the efficient enantioselective synthesis of the very crowded, biologically active, sesquiterpenes herbertenediol, enokipodin A, and enokipodin B.

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“…266 In a second article, the same author and his group obtained (-)herbertenediol 448, mastigophorene A 449 and mastigophorene B 450, which exhibit neurotrophic properties (Scheme 111). 267 Chiral enamine 443 was alkylated and hydrolysed to give 444.…”

Section: Scheme 110mentioning

confidence: 97%