Bioactive Dimeric Abietanoid Peroxides from the Bark of Cryptomeria japonica

Abstract

Three new dimeric abietane-type diterpenoids, abieta-6,8,11,13-tetraen-12-yl 12-hydroxyabieta-8,11,13-trien-7α-yl peroxide (1), abieta-6,8,11,13-tetraen-12-yl 12-hydroxyabieta-8,11,13-trien-7β-yl peroxide (2), and 12-hydroxyabieta-8,11,13-trien-7β-yl 7-oxoabieta-5,8,11,13-tetraen-12-yl peroxide (3), together with four known abietane-type diterpenoids (4–7) were isolated from the methanol extract of the bark of Cryptomeria japonica. Their structures were elucidated on the basis of spectroscopic analysis and comparison of NMR data with those of known analogues. At a concentration of 50 μM, compounds 1, 2, and 3 showed 26.2%, 23.6%, and 35.7% inhibition towards xanthine oxidase enzyme, respectively. In addition, compound 3 also showed 24.9% inhibition toward angiotensin-converting enzyme (ACE).

Terpenoids of the Swamp Cypress Subfamily (Taxodioideae), Cupressaceae, an Overview by GC-MS

“…The diterpenoid constituents of Cryptomeria japonica and Taxodium distichum have been studied more extensively [24,25,26,27,28,29,31,32,33,34,35,38,39,40,41,42,48] and references therein]. However, none of these earlier studies reported the natural product compositions of the total resin/plant extracts, but instead the mixtures were separated by liquid or high-pressure liquid chromatography (LC or HPLC), followed by structure determination of each compound by NMR, HRMS for elemental composition, and sometimes MS (underivatized by direct insertion probe).…”

“…The identification of cymenylferruginol ( a26 ), a triterpenoid like the chamaecydins, in both the extant and fossil resins is of interest because natural product chemists are identifying numerous dimer terpenoids, i.e., mono-to-diterpenoid, sesqui-to-diterpenoid and diterpenoid dimers, in extant plants [25,26,36,41,48]. Therefore, the formation mechanism is for example ferruginol reacting at C-7 with cymene to produce 7-cymenylferruginol, 6-deoxotaxodione reacting at C-7 and C-14 with sabinene or thujene to form chamaecydin, cadinols reacting with ferruginol at C-7 to yield the various sesquaterpenoids, or peroxidation of ferruginol to dimers [26,41,48,72,73]. Some of these natural products, if adequately concentrated in the extant biomass, may become preserved as tracers in the geological record, as for example cymenylferruginol reported here.…”

Biogenetic and biomimetic synthesis of natural bisditerpenoids: hypothesis and practices

“…Five abietane-type diterpenoid homodimers with a peroxide linkage, 246–250 , were isolated from Cryptomeria japonica . 147,148 From the same plant, japonicinol A ( 251 ) is a heterodimeric analog of 246–250 bearing a peroxide linkage. 104 The first example of a biscembranoid connected by a peroxide group, bischerbolide peroxide ( 252 ), was isolated from the Formosan soft coral Sarcophyton cherbonnieri .…”