AIBN-initiated radical addition of gem-difluorinated alkyl iodides to alkynes and the Pd-catalyzed Sonogashira coupling reaction of E-phenyl difluoromethylene vinylic iodides with terminal alkynes

The addition of gem-difluorinated alkyl iodides to alkynes initiated by AIBN neatly gave the corresponding difluoromethylene vinyl iodides among which the stereoselectivity of aromatic acetylenes was high. The further coupling reaction of E-phenyl difluoromethylene vinyl iodides with terminal alkynes in the presence of catalytic palladium afforded the substituted difluorinated enynes.     

Biomimetic Asymmetric Reduction of Quinazolinones with Chiral and Regenerable NAD(P)H Models

A facile approach to chiral dihydroquinazolinone derivatives has been described via biomimetic asymmetric reduction of quinazolinones with chiral and regenerable NAD(P)H models. The utility of this method was demonstrated by a concise synthesis of the bromodomain protein divalent inhibitor.     

Investigations on Preparation,Crystal Structure and Thermal Stability of Bis(O-ethylcarbonodithiolato-S,S′)(1,10-phenanthroline-N~1,N~(10))cobalt(II) Complex:[Co(Et-XA)_2·phen]·H_2O (XA=xanthate)

IntroductionTheincreasingcommercialvalueoftransitionmetalcomplexesofxanthateshasarousedconsiderableinterestintheirchemistry .Whiletheiranalyticalapplicationsarewellknown ,1theyarenowfindingextensiveuseinvulcan izationofrubber ,frothfloatationprocessforconcentrationofsulphideores ,asantioxidants ,lubricants ,2 ,3andhavebeenfoundtopossessfungicidalandinsecticidalactivi ties .4 Recently ,molecularrecognitionbetweenhostandguestmolecules ,inclusionphenomenaandnoncovalentmolecularinteractionarefunda…     

Preparative SEC column packed with microporous particles prepared from cellulose

New microporous particles with large pore size (mean pore diameter of 820 nm) are successfully prepared from a mixture of cellulose and konjac glucomannan (RC-KGM3) in 1.5 M NaOH-0.65 M thiourea aqueous solution by coagulating with 5 weight percentage (wt%) CaCl(2), and then 2 wt% HCl aqueous solution. A preparative size-exclusion chromatographic (SEC) column packed with the gel particles is used for the fractionation of a dextran in water. The exclusion limit and fractionation range of the stationary phase are molecular masses of 125 yen 104 g/mol and 5.6 yen 104 to 125 yen 104 g/mol, respectively. The dextran [dextran 50, weight-average molecular mass (M(w)) = 40.1 yen 104 g/mol, polydispersity index (d) = 3.5] is fractionated by the preparative SEC column to obtain six fractions, and four of them are refractionated twice by the same preparative SEC column. The refractionated samples F-3-3 and F-4-3 are characterized by analytical SEC combined with laser light scattering and light scattering to obtain M(w) of 91.8 and 61.9 yen 104 g/mol, as well as d of 1.3 and 1.4, respectively. The results indicate that the fractions having narrow molecular mass distribution are satisfactorily prepared with the SEC column. The described SEC column can be successfully used to fractionate polymers in aqueous solution.     

添加剂铜和银离子对MnO2催化燃烧CH4的影响

催化燃烧法，由于起燃温度低、去除率高、适用氧浓度范围大、无二次污染、燃烧缓和等，是国内外治理有机废气时，回收利用能量最有效的方法之一［１］．但目前用于该过程的催化剂中均含有来源有限、价格昂贵的贵金属铂或钯［２］．因此，寻找来源丰富、价格低廉、性能相当...     

Theoretical Study on the Isomerization Mechanism of Enol Ester from 2-Acyl-1, 3-cyclohexanediones

The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a), respectively. The base catalytic effects of solvent triethylamine on these two reactions were also evaluated. It is demonstrated that path B is more preferable than path a due to low barrier height for the rate-determining step.     

Boomerang‐Type Substitution Reaction: Reactivity of Fullerene Epoxides and a Halofullerenol

The C_s‐symmetric fullerene chlorohydrin C₆₀(Cl)(OH)(OOtBu)₄ reacts with 4‐dimethylaminopyridine (DMAP) and 1,4‐diazabicyclo[2.2.2]octane (DABCO) to yield two isomers with the formula C₆₀(O)(OOtBu)₄ in good yields. These isomers differ with respect to the location of the epoxy functionality. The one from DMAP is C_s symmetric, whereas that from DABCO is C₁ symmetric with the epoxy group on the central pentagon. Two different mechanisms are proposed to explain the chemoselectivity of these reactions. The reaction with DMAP involves single‐electron transfer as the key step; DMAP acts as the electron donor. A combination of an oxygen‐atom shift and S_N2′′ processes (boomerang substitution) are responsible for the formation of isomer with DACBO. Various related reactions support the proposed mechanisms. The structures of new fullerene derivatives were determined by spectroscopy, single‐crystal X‐ray analysis, and chemical correlation experiments.     

On-line Separation and Detection of Peptides by Capillary Electrophoresis / Electrospray FT-ICR-MS

Recently, capillary electrophoresis/electrospray ionization mass spectrometry (CE/ESI- MS) has been rapidly developed as a powerful analytical tool for charged species ranged from small molecules such as carboxylic acids1, phenolic compounds2, metal species3, tetramines4, herbicides5, drugs and drug metabolites6 to peptides and proteins7, 8. The ESI mode has proven to be sensitive, versatile and relatively easy to use in combination with CE. CE confers rapid analysis and efficient separ…     

Three New Triterpenoids from Lycopodium japonicum Thunb

Three new triterpenoids, (3β,8β,14α,21α)‐26,27‐dinoronocerane‐3,8,14,21‐tetrol ( 1 ), (3β,8β,14α,21β)‐26,27‐dinoronocerane‐3,8,14,21‐tetrol ( 2 ), and lycopodiin A ( 3 ), together with four known compounds, lycoclavanol ( 4 ), lycoclaninol ( 5 ), α‐onocerin ( 6 ), and 3‐epilycoclavanol ( 7 ), were isolated from Lycopodium japonicum Thunb (Lycopodiaceae). Their structures were established by means of spectroscopic analyses. Compounds 3 and 7 showed moderate antitumor activity. Compounds 4 and 6 exhibited acetylcholinesterase inhibition activity.