A simple total synthesis of (+)-ferruginol, (+)-sempervirol, and (+)-podocarpa-8(14)-en-13-one.
Takashi Matsumoto,Shuji Usui +1 more
TLDR
The Wittig reaction of (R)-(−)-α-cyclocitral with (3-isopropyl-4-methoxybenzyl)-, (4-isooperopyl)-3methoxypodocarpa-8, 11, 13-triene as mentioned in this paper gave (+)-podocarpas-8(14)-en-13-one, a versatile intermediate for natural diterpene synthesis.Abstract:
The Wittig reaction of (R)-(−)-α-cyclocitral with (3-isopropyl-4-methoxybenzyl)-, (4-isopropyl-3-methoxybenzyl)-, and (3-methoxybenzyl) triphenylphosphonium chloride afforded the styryl derivatives which were partially hydrogenated to the corresponding dihydro derivatives (18, 26, and 27). Intramolecular cyclization of 18 and 26 with anhydrous aluminium chloride followed by demethylation with boron tribromide gave (+)-ferruginol and (+)-sempervirol. The similar cyclization of 27 gave (+)-13-methoxypodocarpa-8, 11, 13-triene. This was reduced with lithium in liquid ammonia in the presence of ethanol and then treated with dilute hydrochloric acid to give (+)-podocarpa-8(14)-en-13-one, a versatile intermediate for natural diterpene synthesis.read more
Citations
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Aromatic abietane diterpenoids: their biological activity and synthesis
TL;DR: The biological properties of natural abietane-type diterpenoids with an aromatic C ring are reviewed and an overview of the synthetic studies of this group of abietanes, including dehydroabietic acid, callitrisic acid and ferruginol is presented.
Journal ArticleDOI
Enantio- and diastereoselective stepwise cyclization of polyprenoids induced by chiral and achiral LBAs. A new entry to (-)-ambrox, (+)-podocarpa-8,11,13-triene diterpenoids, and (-)-tetracyclic polyprenoid of sedimentary origin.
TL;DR: An enantio- and diastereoselective stepwise cyclization of polyprenoids induced by Lewis acid-assisted chiral Brønsted acids (chiral LBAs) and achiralLBAs and the importance of the nucleophilicity of the internal terminator in polyPrenoids for the relative stereocontrol in subsequent cyclization are demonstrated.
Journal ArticleDOI
Enantioselective Biomimetic Cyclization of Homo(polyprenyl)arenes. A New Entry to (+)-Podpcarpa-8,11,13-triene Diterpenoids and (−)-Tetracyclic Polyprenoid of Sedimentary Origin
Journal ArticleDOI
Asymmetric alkylation of α-aryl substituted carbonyl compounds by means of chiral phase transfer catalysts. Applications for the synthesis of (+)-podocarp-8(14)-en-13-one and of (−)-Wy-16,225, a potent analgesic agent
Wim Nerinckx,Maurits Vandewalle +1 more
TL;DR: Asymmetric induction in the alkylation (alkyl halides and enones) of α-aryl substituted ketones, esters and lactones by means of CPTC has been evaluated as discussed by the authors, and the potential of the method is illustrated by the asymmetric synthesis of (+)-podocarp-8(14)-ene-13-one (13 ) and of (−)-Wy-16,225 (10 ), a bridged aminotetralin with potent analgesic properties.
Journal ArticleDOI
Synthesis of (+)-podocarp-8(14)-en-13-one and methyl-(+)-13-oxo-podocarp-8(14)-en-18-oate from abietic acid
TL;DR: In this article, an efficient method for the preparation of (+)-podocarp-8(14)-en-13-one 6 and methyl-(+)-13-oxo-podocar-8 (14)en-18-oate 8 from abietic acid is described.
References
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Synthesis of Taxodione, Royleanone, Cryptojaponol, and Methyl 11-Hydroxy-12-methoxy-7-oxoabieta-8,11)13-trien-18-oate
TL;DR: In this article, the C-11 position of methyl 12-hydroxyabieta-8,11,13-trien-18-oate (II) and ferruginol (XXXII) were successfully oxidized using benzoyl peroxide.
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A Convenient Synthesis of (±)-Taxodione, (±)-Ferruginol, and (±)-Sugiol
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