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Phytogrowth-inhibitory and antifungal constituents of Helianthella quinquenervis.

Investigation on the roots of Helianthella quinquenervis (Hook.) A. Gray (Asteraceae), led to the isolation of one new benzofuran (6-methoxy-tremetone (1)) and a new prenylacetophenone (4-beta-D-(glucopyranosyloxy)-3-[3-methoxy-trans-isopenten-1 -yl] acetophenone (3)). In addition, 6-hydroxy-3-methoxytremetone (2), encecalin (6), euparin (5), demethylencecalin (4), and angelic acid were obtained. Structural assignments of the isolated compounds were based on spectroscopic and spectrometric analysis. Natural products 1-4 showed marginal cytotoxicity against three human tumor cell lines [MCF-7, A-549, and HT-29]. Compounds 4 and 6 inhibited the radicle growth of Amaranthus hypochondriacus and Echinochloa crusgalli. Furthermore, substances 4-6 exhibited antifungal activity against Trichophyton mentagrophytes.

Animals↗

Sucrose esters and xanthone C-glycosides from the roots of Polygala sibirica.

Six new sucrose esters, sibiricoses A(1)-A(6) (1-6), two new xanthone C-glycosides, sibiricaxanthones A (7) and B (8), and a new acetophenone glycoside, sibiricaphenone (9), were isolated from the roots of Polygala sibirica together with six known glycosides. The structures of new compounds were elucidated on the basis of chemical and spectroscopic evidence. The structure of the known xanthone glycoside, polygalaxanthone III (10), was revised.

Carbohydrate Sequence↗

Norrish type II photochemical reaction of an aryl ketone on a monolayer-protected gold nanocluster. Development Of a probe of conformational mobility

A Norrish type II reaction of an aryl ketone monolayer-protected colloid was investigated for the first time. Photolysis of mercaptoundecanophenone-modified gold colloid, MUP-MPC, generates free acetophenone in solution and the nonene-modified MPC via the triplet excited state and the 1,4-biradical intermediate. The reaction is being developed as a probe of conformational mobility in these unique environments.

Journal Article↗

Practical synthesis of optically active styrene oxides via reductive transformation of 2-chloroacetophenones with chiral rhodium catalysts.

[reaction: see text] A practical method for the synthesis of optically active styrene oxides has been developed via formation of optically active 2-chloro-1-phenylethanols generated by reductive transformation of ring-substituted 2-chloroacetophenones. The optically active alcohols with up to 98% ee are obtainable from the asymmetric reduction of acetophenones with an S/C = 1000-5000 with a formic acid triethylamine mixture containing a well-defined chiral Rh complex, CpRhCl[(R,R)-Tsdpen].

Journal Article↗

Palladium-catalyzed arylation of ketone enolates: an expeditious entry to tamoxifen-related 1,2,2-triarylethanones.

[reaction: see text]. After a rigorous study on the effect of several catalytic systems, a simple, high yielding procedure for the preparation of 1,2,2-triarylethanones, skeletal analogues of tamoxifen, is presented. Apart from the economic and environmental advantages involved, this palladium-catalyzed arylation of deoxybenzoin enolates features a lack of ortho-arylation side reactions. In addition, an alternative approach from acetophenones to the target triarylethanone system is also announced.

Alkylation↗

Asymmetric transfer hydrogenation of prochiral ketones in aqueous media with new water-soluble chiral vicinal diamine as ligand.

[reaction: see text] An easily accessible water-soluble chiral o-sulfonated 1,2-diphenylethlenediamine 2 and its mono-N-tosylated derivative 3 were synthesized for the first time. The ruthenium-complex-catalyzed reduction of prochiral ketones in aqueous media has been examined by using 3 as ligand and sodium formate as the source of hydrogen. The asymmetric transfer hydrogenation of omega-bromo acetophenones was achieved, in which only formate displacement occurred when formic acid/triethylamine azeotrope was used as the hydrogen donor.

Journal Article↗

Bhc-diol as a photolabile protecting group for aldehydes and ketones.

[reaction: see text] 6-Bromo-4-(1,2-dihydroxyethyl)-7-hydroxycoumarin (Bhc-diol) can be used under simulated physiological conditions as a photoremovable protecting group for aldehydes and ketones. The single- and two-photon-induced release of benzaldehyde, piperonal, acetophenone, and cyclohexanone is demonstrated.

Journal Article↗

Cycloruthenated primary and secondary amines as efficient catalyst precursors for asymmetric transfer hydrogenation.

[reaction: see text] Ruthenacycles obtained by cyclometalation of enantiopure aromatic primary or secondary amines with [(eta6-benzene)RuCl2]2 or with [(eta6-p-cymene)RuCl2]2 are efficient catalysts for asymmetric transfer hydrogenation (TOF up to 190 h(-1) at room temperature). Enantioselectivities in the transfer hydrogenation of acetophenone ranged from 38% to 89%. It is possible to prepare the catalysts in situ, which allows the use of high throughput experimentation.

Journal Article↗

Asymmetric hydrogenation of isobutyrophenone using a [(Diphosphine) RuCl2 (1,4-diamine)] catalyst.

[reaction: see text] The use of three chiral 1,4-diamines in the [(diphosphine) RuCl(2) (diamine)] catalyst system is demonstrated in the hydrogenation of acetophenone. The use of a 1,4-diamine offers unique properties that allow tuning of the catalyst system. These include the first example of the use of a racemic diamine in combination with a chiral phosphine, which gives 95% ee in the hydrogenation of isobutyrophenone.

Journal Article↗

Asymmetric transfer hydrogenation of aryl ketones catalyzed by salt-free two samarium centers supported by a chiral multidentate alkoxy ligand.

[reaction: see text] We synthesized a chiral multidentate ligand, (R,R,R,R)-N,N,N',N'-tetra(2-hydroxy-2-phenylethyl)-1,3-xylylene diamine [(R)-2], which can support two metals at adjacent positions. Asymmetric transfer hydrogenation of acetophenone and its derivatives was conducted by using salt-free bimetallic lanthanoid complexes of (R)-2, and the combination of two samarium atoms and (R)-2 was found to be the best catalyst system for asymmetric transfer hydrogenation of aryl ketones in high enantioselectivity (up to >99% ee).

Journal Article↗

Synthetic applicability and in situ recycling of a B-methoxy oxazaborolidine catalyst derived from cis-1-amino-indan-2-ol.

A procedure is described that greatly simplifies the use of an oxazaborolidine catalyst derived from (1R,2S) cis-1-amino-indan-2-ol. This B-OMe catalyst has been employed in the asymmetric reduction of a number of structurally diverse prochiral ketones, in particular the reduction of alpha-amino acetophenone and its derivatives. A method for reducing the effective catalyst loading by "in situ recycling" is also presented. [structure: see text]

Amino Alcohols↗

A new approach to difficult Fischer synthesis: the use of zinc chloride catalyst in triethylene glycol under controlled microwave irradiation.

[reaction: see text]. Application of triethylene glycol with catalytic quantity of zinc chloride (ZnCl2/TEG) is described as a new and efficient reaction medium for a difficult Fischer synthesis, leading to sensitive indoles. Transformation of the 3-acetyl-1-methylthiocycloalka[c]pyridine phenylhydrazones and p-methoxyphenylhydrazones into the 2-(2-pyridyl)indoles and 5-methoxy-2-(2-pyridyl)indoles, which are the synthons in our total synthesis of the sempervirine-type alkaloids, is carried out under controlled microwave irradiation in dry zinc chloride solution (0.16 M) in TEG. This protocol produces indoles from acetophenone or cyclohexanone via their phenylhydrazones in excellent yields.

Journal Article↗

Electronic effects of ring substituents on triplet benzylic biradicals.

[reaction: see text] UV irradiation of alpha-(o-alkylphenyl)acetophenones with a methoxy or cyano substituent para to the o-alkyl group of the alpha-aryl ring has revealed that a methoxy group slightly increases the stereoselectivity but not the quantum yield of indanol formation, whereas a cyano group greatly lowers both diastereoselectivity and quantum efficiency, confirming the likelihood that hydrogen-bonding of the hydroxy group to the alpha-phenyl ring plays an important role in the cyclization of the photogenerated triplet 1,5-biradical intermediates.

Journal Article↗

Direct electrophilic alpha-fluorination of imines: efficient synthesis of mono- and difluoroimines.

[reaction: see text] A mild and efficient procedure to synthesize alpha-fluoro- and alpha,alpha-difluoroimines was developed. Various N-alkylimines derived from acetophenones were successfully monofluorinated using NFSI (N-fluorobenzenesulfonimide) in a mixture of CH(3)CN and DMF at 0 degrees C. Alternatively, the same procedure without DMF gave rise to difluorinated imines when performed at room temperature. The obtained alpha- and alpha,alpha-difluorinated imines were subsequently reduced to give the corresponding beta-fluoro- and beta,beta-difluoroamines in good yield.

Journal Article↗

Metabolism of alkylbenzenes, alkanes, and other hydrocarbons in anaerobic bacteria.

Aromatic and aliphatic hydrocarbons are the main constituents of petroleum and its refined products. Whereas degradation of hydrocarbons by oxygen-respiring microorganisms has been known for about a century, utilization of hydrocarbons under anoxic conditions has been investigated only during the past decade. Diverse strains of anaerobic bacteria have been isolated that degrade toluene anaerobically, using nitrate, iron(III), or sulfate as electron acceptors. Also, other alkylbenzenes such as m-xylene or ethylbenzene are utilized by a number of strains. The capacity for anaerobic utilization of alkylbenzenes has been observed in members of the alpha-, beta-, gamma- and delta-subclasses of the Proteobacteria. Furthermore, denitrifying bacteria and sulfate-reducing bacteria with the capacity for anaerobic alkane degradation have been isolated, which are members of the beta- and delta-subclass, respectively. The mechanism of the activation of hydrocarbons as apolar molecules in the absence of oxygen is of particular interest. The biochemistry of anaerobic toluene degradation has been studied in detail. Toluene is activated by addition to fumarate to yield benzylsuccinate, which is then further metabolized via benzoyl-CoA. The toluene-activating enzyme presents a novel type of glycine radical protein. Another principle of anaerobic alkylbenzene activation has been observed in the anaerobic degradation of ethylbenzene. Ethylbenzene in denitrifying bacteria is dehydrogenated to 1-phenylethanol and further to acetophenone; the latter is also metabolized to benzoyl-CoA. Naphthalene is presumably activated under anoxic conditions by a carboxylation reaction. Investigations into the pathway of anaerobic alkane degradation are only at the beginning. The saturated hydrocarbons are most likely activated by addition of a carbon compound rather than by desaturation and hydration, as speculated about in some early studies. An anaerobic oxidation of methane with sulfate as electron acceptor has been documented in aquatic sediments. The process is assumed to involve a reversal of methanogenesis catalyzed by Archaea, and scavenge of an electron-carrying metabolite by sulfate-reducing bacteria. Among unsaturated non-aromatic hydrocarbons, anaerobic bacterial degradation has been demonstrated and investigated with n-alkenes, alkenoic terpenes and the alkyne, acetylene.

Bacteria, Anaerobic↗

Synthesis and anti-inflammatory effect of chalcones and related compounds.

PURPOSE: Mast cell and neutrophil degranulations are the important players in inflammatory disorders. Combined with potent inhibition of chemical mediators released from mast cells and neutrophil degranulations, it could be a promising anti-inflammatory agent. 2',5'-Dihydroxychalcone has been reported as a potent chemical mediator and cyclooxygenase inhibitor. In an effort to continually develop potent anti-inflammatory agents, a novel series of chalcone, 2'- and 3'-hydroxychalcones, 2',5'-dihydroxychalcones and flavanones were continually synthesized to evaluate their inhibitory effects on the activation of mast cells and neutrophils and the inhibitory effect on phlogist-induced hind-paw edema in mice. METHODS: A series of chalcones and related compounds were prepared by Claisen-Schmidt condensation of appropriate acetophenones with appropriate aromatic aldehyde and the anti-inflammatory activities of these synthetic compounds were studied on inhibitory effects on the activation of mast cells and neutrophils. RESULTS: Some chalcones showed strong inhibitory effects on the release of beta-glucuronidase and histamine from rat peritoneal mast cells stimulated with compound 48/80. Almost all chalcones and 4'-hydroxyflavanone exhibited potent inhibitory effects on the release of beta-glucuronidase and lysozyme from rat neutrophils stimulated with formyl-Met-Leu-Phe (fMLP). Some chalcones showed potent inhibitory effects on superoxide formation of rat neutrophils stimulated with fMLP/cytochalasin B (CB) or phorbol myristate acetate (PMA). 2',3-Dihydroxy-, 2',5'-dihydroxy-4-chloro-, and 2',5'-dihydroxychalcone showed remarkable inhibitory effects on hind-paw edema induced by polymyxin B in normal as well as in adrenalectomized mice. CONCLUSIONS: These results indicated that the anti-inflammatory effects of these compounds were mediated, at least partly, through the suppression of chemical mediators released from mast cells and neutrophils.

Animals↗

The anomalous hydrolytic behavior of 1-phenylvinyl phosphate.

The kinetics of hydrolysis of 1-phenylvinyl phosphate, 1, were studied over a pH range of 1 to 8.3 and over a pD range of 1 to 5.6 at 25 degrees C and mu = 0.5 M with sodium chloride. The hydrolytic behavior of 1 was found to differ, in many respects, from that of alkyl and aryl phosphomonoesters. First, the rates of hydrolysis of 1 were extremely rapid and, in the hydronium ion-catalyzed region, gave a solvent deuterium isotope effect (kH/kD) of 3.20. Also, the 1H-NMR spectrum of acetophenone formed upon complete hydrolysis of 1 in D2O (pD 1.2) revealed that only one deuterium atom was incorporated into the methyl group. Hence, the evidence was consistent with a rate-limiting and nonreversible proton transfer from the solvent to 1. In addition, using an H2 18O labeling study in conjunction with 31P-NMR analysis, the hydrolytic mechanism appeared to involve nucleophilic attack by water at both the alpha-carbon and the phosphorus atom with concurrent C-O and P-O bond fission. Second, in the pH region where the monoanionic species of 1 predominated, buffers had a pronounced catalytic effect on the hydrolysis rate; there appeared to be a normal solvent deuterium isotope effect; and the rate constant, k' o, showed a positive deviation from the established Brønsted relationship. The dissimilarities between 1 and alkyl and aryl phosphomonoesters supported the involvement of an alternate dephosphorylation pathway.(ABSTRACT TRUNCATED AT 250 WORDS)

Algorithms↗

The effects of phthalimide and saccharin derivatives on low-density lipoprotein (LDL) and high-density lipoprotein (HDL) receptor activity and related enzyme activities.

The hypolipidemic agents, phthalimide, saccharin, o-(N-phthalimido) acetophenone, N-(p-chlorobenzoyl) sulfamate, and o-chlorobenzylsulfonamide affected low-density lipoprotein (LDL) and high-density lipoprotein (HDL) receptor activity and lipoprotein degradation. In isolated rat hepatocytes, rat aorta foam cells, and human fibroblasts, LDL receptor activity, which is dependent on apo-B and -E, was inhibited by the drugs in a dose-dependent manner. LDL degradation was accelerated in the hepatocytes, while it was inhibited in aorta cells and fibroblasts. The drugs enhanced HDL receptor activity, dependent on apo-E and -A1, and HDL degradation in the hepatocytes, whereas in fibroblasts and aorta cells HDL receptor binding and degradation were suppressed. In parallel, activities of acyl CoA acyl transferase, sn-glycerol-3-phosphate acyl transferase, and heparin-induced lipoprotein lipase decreased and activities of HMG-CoA reductase and cholesterol oleate-ester hydrolase increased. In fibroblasts the presence of drugs enhanced HDL binding of intracellular cholesterol. In vivo studies demonstrated that phthalimide and saccharin treatment enhanced the clearance of HDL and decreased the clearance of LDL from the serum of rats. The results suggest that the mode of action of the agents is to modulate the lipoprotein receptor and, thereby, the clearance of lipids from peripheral tissue as part of the hypolipidemic activity.

Animals↗