Production and degradation mechanism of theacitrin C, a black tea pigment derived from epigallocatechin-3-O-gallate via a bicyclo[3.2.1]octane-type intermediate

Black tea is rich in polyphenols and has been shown to have various health benefits; however, its components have not yet been clarified in detail. Enzymatic oxidation of epigallocatechin-3-O-gallate, the most abundant polyphenol in tea, is thought to contribute significantly to the production of black tea polyphenols. We identified theacitrin C, an unstable black tea pigment, as an enzymatic oxidation product of epigallocatechin-3-O-gallate. Degradation of theacitrin C afforded theacitrinin A and 2,3,5,7-tetrahydroxychroman-3-O-gallate. Furthermore, theacitrinin B, which was isolated from black tea, is deduced to be a degradation product of theacitrin A, the desgalloyl analogue of theacitrin C. The structures of theacitrinins A and B were elucidated based on spectroscopic data. This is the first time that a degradation product of theacitrin has been isolated from black tea. We also examined the influence of esterification of the epigallocatechin C-3 hydroxyl group on the decomposition of bicyclo[3.2.1]octane-type intermediates.     

The first synthesis of phosphonoacrolein. Application to Diels-Alder reaction as heterodiene

The first synthesis of phosphonoacrolein 3 was made in quantitative yield by acidic treatment of beta-ethoxy-alpha-(methoxymethyl)vinylphosphonate 2, derived from a beta-ethoxy-alpha-phosphonovinyl anion and MOMCl. The phosphonoacrolein 3 easily underwent a hetero-Diels-Alder reaction with electron-rich alkenes 4a-f or alkynes 9a-c under mild conditions, and phosphono-substituted pyrans 5a-d, 6e,f or pyranopyrans 11a-c were obtained in good to excellent yields. The reaction of 3 with cyclopentadiene and cyclohexadiene led to mixtures of [2 + 4] and [4 + 2] cycloadducts 7a, 8a and 7b, 8b in modest yields. The cycloaddition reaction between 3 and pyranopyran 13 or dibromocarbene and 13 resulted in [4 + 2] or [2 + 1] cycloadducts 14 or 15 in good yields.     

Iridoids and anthraquinones from the Malaysian medicinal plant,Saprosma scortechinii (Rubiaceae)

A further investigation of the leaves and stems of Saprosma scortechinii afforded 13 compounds, of which 10 are new compounds. These were elucidated as the bis-iridoid glucosides, saprosmosides G (1) and H (2), the iridoid glucoside, 6-O-epi-acetylscandoside (3), and the anthraquinones, 1-methoxy-3-hydroxy-2-carbomethoxy-9,10-anthraquinone (4), 1-methoxy-3-hydroxy-2-carbomethoxy-9,10-anthraquinone 3-O-beta-primeveroside (5), 1,3-dihydroxy-2-carbomethoxy-9,10-anthraquinone 3-O-beta-primeveroside (6), 1,3,6-trihydroxy-2-methoxymethyl-9,10-anthraquinone (7), 1-methoxy-3,6-dihydroxy-2-hydroxymethyl-9,10-anthraquinone (8), 1,3,6-trihydroxy-2-hydroxymethyl-9,10-anthraquinone 3-O-beta-primeveroside (9), and 3,6-dihydroxy-2-hydroxymethyl-9,10-anthraquinone (10). Structure assignments for all compounds were established by means of mass and NMR spectroscopies, chemical methods, and comparison with published data. The new anthraquinones were derivatives of munjistin and lucidin.     

A new toxic neoanisatin derivative from the pericarps of Illicium majus

A new toxic neoanisatin-derivative (1) was isolated from the pericarps of Illicium majus. The structure of this compound was elucidated by spectroscopic data, including the 2D COSY NMR technique. The toxicity of compound 1 is also described.     

Biflavanones, diterpenes, and coumarins from the roots of Stellera chamaejasme L

A new biflavanone (1) with a C-3/C-3" linkage, a new daphnane-type diterpene (2) acylated by an unsaturated fatty acid, and a new coumarin glycoside (3), along with six lignans, two phenylpropanoids, five flavonoids, two diterpenes, and three coumarins were isolated from the roots of Stellera chamaejasme L. (Thymelaeaceae). Elucidation of these secondary metabolites of S. chamaejasme L. supplied strong chemical verification of the close taxonomic relationships among the genera Stellera, Daphne, and Wikstroemia, all of which belong to the family Thymelaeaceae.     

Alkaloids, diarylheptanoid and naphthalene carboxylic acid ester from Rhoiptelea chiliantha.

Two pyrrolidine alkaloids (1, 2) were isolated from the fruits of Rhoiptelea chiliantha Diel et Hand.-Mazz. (Rhoipteleaceae). A diphenyl ether-type diarylheptanoid (3), and a naphthalene carboxylic acid methyl ester (4) which is biogenetically-related to juglone were isolated from the branches of the same plant. Their chemical structures were elucidated on the basis of spectroscopic analysis and chemical evidence.     

Association of tannins and related polyphenols with the cyclic peptide gramicidin S

The association of 10 different tannins and related polyphenols with gramicidin S, a cyclic peptide having a rigid beta-turn structure, has been examined using 1H-NMR spectroscopy. In the presence of pentagalloylglucose and epigallocatechin-3-O-gallate, the proton signals due to proline and the adjacent phenylalanine moieties selectively shifted to up field, suggesting a regioselective association with the beta-turn structure. The association was also supported by the observation of intermolecular nuclear Overhauser effects between epigallocatechin-3-O-gallate and the peptide. In contrast, ellagitannins, biogenetically derived from pentagalloylglucose, showed small and non-selective chemical shift changes, suggesting that interaction with these tannins is relatively weak. The hydrophobicity of the tannin molecules and the steric hindrance of the interaction site are thought to be important in the association.     

Excluded volume,bag constant and hadron-quark phase transition

The model of hadron-quark phase transitions proposed by Cleymans et al. is modified by taking into account the fact that the nuclear repulsive force is operative between a pair of nucleons or a pair of antinucleons but not between a nucleon and an antinucleon. The phase boundary in the temperature (T)-chemical potential (μ) plane is calculated for some values of the bag constantB and the hard core radiusR. Stability of the normal nuclear matter together with the bag picture for the nucleon yields rather stringent bounds forB as functions ofR. The most probable range of values is estimated to beB ^1/4?150～200 MeV being consistent with the estimate from hadron spectroscopy. For this range ofB, it is improbable to realize the broken chiral phase with deconfining constituent quarks and Goldstone pions at someT and μ.     

Rubusuaviins A-F, monomeric and oligomeric ellagitannins from Chinese sweet tea and their alpha-amylase inhibitory activity

Six new ellagitannins herein, rubusuaviins A-F, were isolated from the aqueous acetone extract of Chinese sweet tea (Tien-cha, dried leaves of Rubus suavissimus S. LEE) together with seven known tannins. Rubusuaviin A was characterized as 1-O-galloyl-2,3-O-(S)-HHDP-4,6-O-(S)-sanguisorboyl-beta-D-glucopyranose. Rubusuaviins B, C, and E are dimeric, trimeric, and tetrameric ellagitannins, respectively, in which the sanguisorboyl groups were connected ellagitannin units. Rubusuaviins D and F were desgalloyl derivatives of rubusuaviins C and E, respectively. The inhibition of alpha-amylase activity by rubusuaviins and related ellagitannins was compared. Ellagitannins with beta-galloyl groups at the glucose C-1 positions showed stronger inhibition compared with the alpha-galloyl and desgalloyl compounds. The molecular weight of these compounds was not important for the inhibition of alpha-amylase activity.