Friedelin,D:A-friedo-olean-3,21-dione and 21α-hydroxy-D:A-friedo-olean-3-one from Kokoona zeylanica

Three triterpenes obtained from the inner bark of Kokoona zeylanica have been identified as friedelin, D:A-friedo-olean-3, 21-dione and 21α-hydroxy- D:A-friedo-olean-3-one by spectroscopic properties and chemical interconversions. Their chemotaxonomic significance is emphasized.     

Triterpenes and neoflavonoids of Calophyllum lankaensis and Calophyllum thwaitesii

The petrol extracts of the leaves of Calophyllum lankaensis and C. thwaitesii yielded D:A-friedo-oleanan-3-one, 28-hydroxy-D:A-friedo-oleanan-3-one (canophyllol), 28-oxo-D:A-friedo-oleanan-3-one (canophyllal calozeylanic acid, thwaitesic acid, isothwaitesic acid and apetalactone. Thwaitesic acid and iso-thwaitesic acid are two novel neoflavonoids.     

An unusual m-hydroxyacetophenone and three new chromanone derivatives from Chrysothamnus viscidiflorus

An unusual m-hydroxyacetophenone, named viscidone, and three new chroman-4-one derivatives were isolated from Chrysothamnus viscidiflorus ssp. lanceolatus, which also contained a known p-hydroxyacetophenone derivative. Their structures were determined by spectroscopic (¹H and ¹³C NMR, UV, IR and MS) and chemical means.     

Elaeodendrol and elaeodendradiol,new nor-triterpenes from Elaeodendron glaucum

The isolation of six known and two new D:A-friedooleananes is reported from the bark of Elaeodendron glaucum. The structures of the new nor-triterpenes, elaeodendrol and elaeodendradiol, were established respectively as 17β- hydroxy-28-norfriedelan-3-one and l7β,25-dihydroxy-28-norfriedelan-3-one by a study of the methyl chemical shifts in their ¹H NMR spectra.     

Canthinones from Simaba cuspidata

Two new alkaloids, 8-methoxycanthin-6-one and 3-methoxycanthin-2,6-dione, were isolated from the EtOH extract of the bark of Simaba cuspidata Spruce ex Engl. Elucidation of the structure of the latter compound included ¹³C NMR spectral comparison with 2-methoxypyridine-N-oxide and N-methoxy-2-pyridone.     

3-Oxo-friedelan-20α-OIC acid from gymnosporia emarginata

3-Oxo-friedelan-20α-oic acid, named as maytenonic (polpunonic) acid, has been isolated along with β-amyrin and sitosterol from Gymnosporia emarginata. ¹H and ¹³C NMR signals have been assigned for the structure. X-ray analysis of the single crystal confirmed that the carboxylic acid is α-oriented at C-20 and the D/E rings of this D:A-friedo-oleanane are in chair-chair conformation. ¹³C NMR data of the present compound also enabled the assignment of the C-20α- and β-methyl carbons in friedelin.     

Sulphides and furanones from steam volatile oils of Allium fistulosum and Allium chinense

The constituents of the steam volatile oils from two kinds of Allium fistulosum, A. fistulosum var. caespitosum and A. chinense, have been investigated by GC and spectral techniques (IR, UV, GC/MS, ¹H NMR and ¹³C NMR). The compounds identified from the neutral fraction of each volatile oil included sulphides, thiolanes, alcohols, aldehydes, ketones, furanones and others. Among the sulphur compounds, dipropyl disulphide comprised ca 28% of A. fistulosum oil, ca 23% of A. fistulosum var. caespitosum oil and ca 30% of A. chinense oil. A. fistulosum oil was characterized by a large quantity of tridecan-2-one (ca 52%) and 2,3-dihydro-2-octyl-5-methylfuran-3-one (ca 16%). Also, a large amount of 2,3-dihydro-2-hexyl-5-methylfuran-3-one (ca 20%) was isolated from A. chinense oil.     

21α,26-dihydroxy-D:A-friedooleanan-3-one from Salacia reticulata var. Diandra (celastraceae)

Carbon-13 NMR has been used to detect the position of angular methyl oxygenation and determine the structure of 21α,26-dihydroxy-D:A-friedooleanan-3-one, a new trioxygenated friedooleanane from Salacia reticulata var. diandra and the assignment has been confirmed chemically.     

Three new triterpenoids from Salacia hainanensis Chun et How showed effective anti-α-glucosidase activity

To identify the chemical constituents with hypoglycemic activity in Salacia hainanensis Chun et How, this study was carried out on the roots of S. hainanensis. By means of a bioassay-guided method, three new triterpenoids (2β,3β-dihydroxylup-20(29)-ene [compound 1], 30-hydroxy-D:A-friedo-olean-1-en-3-one [compound 2], and 24,25,26-trihydroxytirucall-7-en-3-one [compound 3]) along with three known compounds (olibanumol J [compound 4], 21α-hydroxy-D:A-friedo-olean-3-one [compound 5], and 29-hydroxy-D:A-friedo-olean-3-one [compound 6]) were isolated from the EtOAc part and were shown to have effective α-glucosidase inhibitory activity. Their structures were established on the basis of spectral analysis, especially according to the data obtained by two dimensional nuclear magnetic resonance spectroscopic and high-resolution mass spectra experiments. All compounds with the exception of compound 2 showed much stronger inhibitory activity against α-glucosidase than did the positive control (acarbose, IC₅₀ 1.02 μM).     

Novel metabolites from the roots of Cadaba natalensis

From an extract of the roots of Cadaba natalensis Sond. the novel macrocyclic dibenzo-diazacyclododecanedione 1 was isolated together with (S)-2-ethyl-2-methyloxazolidin-5-one (2a). In addition, the five known compounds were obtained. Of these, (R)-5-ethyl-5-methyloxazolidin-2-one (3) is reported as a natural product for the first time. The structures of the isolated compounds were elucidated by analysis of the spectral data, 1D NMR (¹H, ¹³C, and DEPT), 2D NMR (COSY, HMQC, HMBC, and NOESY), and HRESIMS, as well as by the comparison with previously reported data.     

Alkaloids of Crinum pratense

From the bulbs of Crinum pratense, collected at flowering, lycorine, 1,2-diacetyllycorine, ambelline, narcissidine, and three phenanthridone alkaloids, viz. hippadine, pratorinine and anhydrolycorin-7-one, were isolated and characterized on the basis of comprehensive spectral analyses (UV, IR, ¹H NMR, ¹³C NMR, MS, [α]_D) and chemical evidence. Among the phenanthridone alkaloids (1–3, only the natural occurrence of hippadine was previously known. Pratorinine is a new phenanthridone alkaloid and anhydrolycorin-7-one was known before only as a synthetic compound. The physiological significance of hippadine is appraised.     

Metabolism of 4-cholesten-3-one to 5α-cholestan-3-one by leaf homogenates

Young leaf homogenates of Digitalis purpurea, Cheiranthus cheiri and Strophanthus kombe' were incubated at 30° for 2 hr with 4-cholesten-3-one-[4-¹⁴C] in a buffered medium containing an NADPH generating system. A single identical metabolite was observed with each tissue. The metabolite was identified by co-chromatography and co-crystallization to constant specific activity as 5α-cholestan-3-one. Leaf homogenates of D. purpurea exhibited the greatest metabolic activity. Addition of non-radioactive progesterone effectively competed with the radioactive substrate, markedly reducing the yield of 5α-cholestan-3-one.     

Two acetylenic compounds from Echinacea pallida roots

Two acetylenic compounds were identified as artifacts in stored roots of Echinacea pallida. Their structures were determined by ¹³C and ¹H NMR spectra as 8-hydroxypentadeca-9E-ene-11,13-diyn-2-one and 8-hydroxypentadeca-9E,13Z-diene-11-yn-2-one.     

Three bridged 14β,26-epoxy-C-homo-pentacyclic triterpenes from Primula rosea

Three new bridged 14β,26-epoxy-C-homo-pentacyclic triterpenes isolated from Primula rosea have been shown to be 14β,26-epoxy-serratane-3,21-dione, 21α-hydroxy-14β,26-epoxy-serratane-3-one and 21β-hydroxy-14β,26-epoxy-serratane-3-one, respectively, on the basis of ¹H NMR, ¹³C NMR and mass spectral and chemical evidence.     

Conformation and dynamics changes of bacteriorhodopsin and its D85N mutant in the absence of 2D crystalline lattice as revealed by site-directed C NMR

¹³C NMR spectra of [3-¹³C]Ala- and [1-¹³C]Val-labeled D85N mutant of bacteriorhodopsin (bR) reconstituted in egg PC or DMPC bilayers were recorded to gain insight into their secondary structures and dynamics. They were substantially suppressed as compared with those of 2D crystals, especially at the loops and several transmembrane α_II-helices. Surprisingly, the ¹³C NMR spectra of [3-¹³C]Ala-D85N turned out to be very similar to those of [3-¹³C]Ala-bR in lipid bilayers, in spite of the presence of globular conformational and dynamics changes in the former as found from 2D crystalline preparations. No further spectral change was also noted between the ground (pH 7) and M-like state (pH 10) as far as D85N in lipid bilayers was examined, in spite of their distinct changes in the 2D crystalline state. This is mainly caused by that the resulting ¹³C NMR peaks which are sensitive to conformation and dynamics changes in the loops and several transmembrane α_II-helices of the M-like state are suppressed already by fluctuation motions in the order of 10⁴-10⁵ Hz interfered with frequencies of magic angle spinning or proton decoupling. However, ¹³C NMR signal from the cytoplasmic α-helix protruding from the membrane surface is not strongly influenced by 2D crystal or monomer. Deceptively simplified carbonyl ¹³C NMR signals of the loop and transmembrane α-helices followed by Pro residues in [1-¹³C]Val-labeled bR and D85N in 2D crystal are split into two peaks for reconstituted preparations in the absence of 2D crystalline lattice. Fortunately, ¹³C NMR spectral feature of reconstituted [1-¹³C]Val and [3-¹³C]Ala-labeled bR and D85N was recovered to yield characteristic feature of 2D crystalline form in gel-forming lipids achieved at lowered temperatures.     

An acyclic diterpene from the brown alga Bifurcaria bifurcata

Structure elucidation and total assignment of the ¹³C NMR spectrum of 12-(S)-hydroxygeranylgeraniol, a new acyclic diterpene from the grown alga Bifurcaria bifurcata, was accomplished through the use of ¹HNMR, ¹³C NMR and 2D NMR spectroscope including 2D long range ¹H-¹³C chemical shift correlations.     

Synthesis of 3β-hydroxy-androsta-5,7-dien-17-one from 3β-hydroxyandrost-5-en-17-one via microbial 7α-hydroxylation

The synthesis of 3β-hydroxy-androsta-5,7-dien-17-one from 3β-hydroxy-androst-5-en-17-one (dehydroepiandrosterone, DHEA) via microbial 7α-hydroxylation has been accomplished. At the first stage, 3β,7α-dihydroxy-androst-5-en-17-one was obtained in high yield (71.2%) using a strain of Gibberella zeae VKM F-2600, which was first applied for DHEA conversion. The further route included the substitution of 7α-hydroxyl group with chlorine followed by a dehydrochlorination stage, and required minimal purifications of the intermediate products. The steroids obtained at every step were characterized by TLC_,¹H NMR, MS, UV- and IR-spectrometry.The combination of microbial and chemical steps ensured 54.6% yield of the target 3β-hydroxy-androsta-5,7-dien-17-one from DHEA and can be applied for obtaining novel vitamin D derivatives.     

Deuterium isotope effects in carbohydrates revisited. Cryoprobe studies of the anomerization and NH to ND deuterium isotope induced 13C NMR chemical shifts of acetamidodeoxy and aminodeoxy sugars

Complete ¹H and ¹³C NMR chemical shift assignments have been generated from a series of acetamidodeoxy and aminodeoxy sugar derivatives. For free sugars, the enhanced sensitivity of an NMR cryoprobe allowed simple 1D and 2D NMR spectra to be obtained from essentially single anomers, before significant mutarotation had occurred. The NMR assignments have been used to characterize deuterium isotope effects on ¹³C chemical shifts measured under conditions of slow NH to ND exchange in single solutions. Within a range of 0 to −0.138 ppm, β, γ, δ, and ζ deuterium isotope effects have been observed, thus providing additional reference data for assignment of the ¹³C NMR spectra of nitrogenous saccharides.     

Acylresorcinols from seed kernels of Myristica dactyloides

A new polyketide 1-(2,6-dihydroxyphenyl)9-(4-hydroxy-3-methoxyphenyl)nonan-1-one and five other polyketides 1-(2,6-dihydroxyphenyl)tetradecan-1-one and malabaricones A-D have been isolated from Myristica dactyloides seeds. ¹³C NMR of the first and the second mentioned compounds are also reported for the first time.     

Synthesis,identification and in vitro biological evaluation of some novel quinoline incorporated 1,3-thiazinan-4-one derivatives

The present study describes the synthesis of two new series of 3-hydroxy-N-(4-oxo-2-phenyl-1,3-thiazinan-3-yl)-8-(trifluoromethyl)quinoline-2-carboxamide derivatives (4a–j) and 3-((7-chloroquinolin-4-ylamino)methyl)-2-phenyl-1,3-thiazinan-4-one derivatives (5a–7j). All the compounds were synthesized in moderate to good yield by one-pot three component cyclo-condensation reaction. The newly synthesized compounds were characterized by FT-IR, ¹H, ¹³C NMR and elemental analysis. The compounds were screened for their in vitro antibacterial activity against a panel of pathogenic bacterial strains, antitubercular activity against Mycobacterium tuberculosis H₃₇Rv and also for their in vitro antimalarial activity against Plasmodium falciparum. Among the synthesized compounds two of them (4f and 5f) showed excellent antibacterial activity against C. tetani at 15.6 μg/mL. Some of them exhibited excellent antitubercular (4f & 5f) and good antimalarial (4f, 5f & 6f) activity compared with the first line drugs.