Cobalt-catalyzed cross-coupling reactions of alkyl halides with allylic and benzylic Grignard reagents and their application to tandem radical cyclization/cross-coupling reactions

Details of cobalt-catalyzed cross-coupling reactions of alkyl halides with allylic Grignard reagents are disclosed. A combination of cobalt(II) chloride and 1,2-bis(diphenylphosphino)ethane (DPPE) or 1,3-bis(diphenylphosphino)propane (DPPP) is suitable as a precatalyst and allows secondary and tertiary alkyl halides--as well as primary ones--to be employed as coupling partners for allyl Grignard reagents. The reaction offers a facile synthesis of quaternary carbon centers, which has practically never been possible with palladium, nickel, and copper catalysts. Benzyl, methallyl, and crotyl Grignard reagents can all couple with alkyl halides. The benzylation definitely requires DPPE or DPPP as a ligand. The reaction mechanism should include the generation of an alkyl radical from the parent alkyl halide. The mechanism can be interpreted in terms of a tandem radical cyclization/cross-coupling reaction. In addition, serendipitous tandem radical cyclization/cyclopropanation/carbonyl allylation of 5-alkoxy-6-halo-4-oxa-1-hexene derivatives is also described. The intermediacy of a carbon-centered radical results in the loss of the original stereochemistry of the parent alkyl halides, creating the potential for asymmetric cross-coupling of racemic alkyl halides.     

Trans-hydrometalation of alkynes by a combination of InCl3 and DIBAL-H: one-pot access to functionalized (Z)-alkenes

[reaction: see text] Triethylborane-induced hydrometalation of alkynes proceeds in an anti manner to afford the corresponding (Z)-alkenylmetal compounds stereoselectively, where dichloroindium hydride would play a key role. A variety of functional groups including hydroxy, carbonyl, and carboxy groups were tolerant under the reaction conditions. Following iodolysis and cross-coupling reaction of the (Z)-alkenylmetal species show the usefulness of this strategy.     

Novel acyl alpha-pyronoids, dictyopyrone A, B, and C, from Dictyostelium cellular slime molds

For the elucidation of the diversity of secondary metabolites of Dictyostelium cellular slime molds, we investigate the constituent of three species of slime molds. From the methanol extract of their fruit bodies, we obtained three novel compounds, dictyopyrone A (1) and B (2) from D. discoideum and D. rhizoposium and dictyopyrone C (3) from D. longosporum. They possess a unique alpha-pyrone moiety with a side chain at the C-3 position. Their relative structures were elucidated by spectral means, and the absolute configuration was confirmed by asymmetric synthesis of 1. Since these compounds were obtained from different species of Dictyostelium slime molds, they may be a type of compound common to this genus.     

Determination of sodium azide in beverages by ion chromatography

A convenient method for determination of sodium azide in beverages using ion chromatography is described. This method combines the specificity for azide with a simple sample preparation using a bubble and trap apparatus that removes any interferences. Sodium azide in a sample was acidified, and the azide was converted to the volatile hydrazoic acid, which was trapped in 2.5 mM sodium hydroxide solution. Determination was performed by isocratic ion chromatography using suppressed conductivity detection. Calibration curves were linear for 0.5 to 20 microg/mL sodium azide and the detection limit was 0.05 microg/mL. Recoveries of sodium azide from spiked samples (10.0 microg/g) were more than 82.6%. The method was then used to analyze various beverages.     

Surprising 1,7-cyclization of vinyl carbonyl ylides generated from reaction of indanetrione with vinyl diazo compounds

Reactions of tricarbonyl compounds with vinyl diazo compounds 2 were carried out. Reaction of 1,2,3-indanetrione with 2a,b,c gave the spiroindan-1,3-dione-2,2′-benzodihydrooxepin 7a,b,c, but not normal products oxirane and dihydrofuran derivatives expected from intermediate vinyl carbonyl ylides 4. Formation of 7 requires isomerization of vinyl carbonyl ylides 4 bearing a (Z)-cyanostyryl group to unstable (E)-form 5 and subsequent cyclization to oxepin 6 followed by a 1,5-hydrogen shift. However, reaction of 2 with six-membered cyclic tricarbonyl compounds 1,2,3-trioxo-2,3-dihydrophenalene 11 and dimethylalloxane 13 gave the dioxole 12 and the dihydrofuran 14, respectively, typical products expected from vinyl carbonyl ylides.     

Ruthenium-catalyzed carbonylative cycloaddition of alpha-keto lactones with alkenes or alkynes: the participation of an ester-carbonyl group in cycloaddition reactions as the two-atom assembling unit

The reaction of benzofuran-2,3-dione derivatives 1 with CO and alkenes (or alkynes) results in a carbonylative [2+2+1] cycloaddition in which the ester-carbonyl group is incorporated into a two-atom assembling unit to give spirolactone derivatives 2. This reaction provides the first example of an ester-carbonyl group participating in a carbonylative cycloaddition reaction.     

Water enables direct use of allyl alcohol for Tsuji-Trost reaction without activators

[reaction: see text] An aqueous biphasic reaction system enables the direct use of allyl alcohol in the Tsuji-Trost reaction without the help of any activating reagents for allyl alcohol. The reaction conditions are neutral to basic, allowing the use of amines as the nucleophile. Theoretical calculations have elucidated the importance of hydration of the hydroxy group for the smooth generation of pi-allylpalladium species.     

Novel trichothecanes, paecilomycine A, B, and C, isolated from entomopathogenic fungus, Paecilomyces tenuipes

Paecilomycine A (1), B (2), and C (3) were isolated from cultivated fruiting bodies of Paecilomyces tenuipes (Isaria japonica), which is a popular entomopathogenic fungus used in folk medicine and health foods in China, Korea, and Japan. The structures of 1-3 were deduced from their spectroscopic data and their absolute configurations were elucidated by preparing their MPA esters. Compound 1 showed activity in the neurotrophic factor biosynthesis in glial cells.     

High-sensitive elemental analysis using multi-parameter coincidence spectrometer: GEMINI-II

In this study, using neutron activation analysis with multi-parameter coincidence method which was developed at Japan Atomic Energy Agency (JAEA), a non-destructive, ultra-high sensitive multi-elemental determination has been realized. The multi-parameter coincidence method is carried out with an array of 19 germanium detectors, GEMINI-II. Using this system, very weak γ-rays emitted from trace amounts of elements can be detected. The iridium concentration has been determined by means of neutron activation analysis with multi-parameter coincidence method for Cuban sediment samples across the K/T boundary strata.     

Improving the properties of the proton exchange membranes by introducing α-methylstyrene in the pre-irradiation induced graft polymerization

New proton exchange membranes (PEMs) were prepared by pre-irradiation induced grafting of α-methylstyrene (AMS)/styrene (STY)/divinylbenzene (DVB) into the crosslinked polytetrafluoroethylene (RX-PTFE) films and successively sulfonated. The new PEMs showed the improved glass transition temperature and chemical stability as compared with the PEMs prepared by pre-irradiation induced grafting of STY/DVB. The balance of the cost, grafting kinetic, thermal properties and the properties of the resulted proton exchange membrane is the key point of this work.