Efficient synthesis of (±)-γ-lycorane employing stereoselective conjugate addition to nitroolefin

(±)-γ-Lycorane 3 was synthesized in 52% overall yield via seven steps from 5 by employing the highly stereoselective nitro-Michael cyclization of 5 to 9 and diastereoselective conjugate addition of aryllithium to a nitroolefin 10 as two key steps.     

Crystalline inclusion compounds constructed through self-assembly of isonicotinic acid and thiocyanato coordination bridges

The synthesis, crystal structures, inclusion ability, and structural robustness of novel crystalline inclusion compounds of [Ni(SCN)2(isoH)2].xG (isoH = isonicotinic acid; G = aromatic guest) are described. The inclusion compounds are constructed by stacking identical 2D host layers that consist of SCN-, isoH, and Ni2+ with van der Waals contact separation. In the layer, two types of rectangular cavities (A-type and B-type) are formed, and the guests are included in the former cavity. The inclusion compounds were categorized into four stacking modes according to the difference in the stacking mode of the layers. A systematic investigation of the crystal structures of the 21 inclusion compounds clarified the close relationship between the molecular structure of the guest and the resultant stacking mode of the layers.     

Construction of arene-fused-piperidine motifs by asymmetric addition of 2-trityloxymethylaryllithiums to nitroalkenes: the asymmetric synthesis of a dopamine D1 full agonist, A-86929

The straightforward methodology for the construction of chiral arene-fused-piperidine motifs using a highly enantioselective addition of 2-trityloxymethylaryllithiums to cyclic and acyclic nitroalkenes has been developed. The versatility of the process was highlighted by the first asymmetric synthesis of a dopamine D1 full agonist, A-86929.     

A direct electrochemical route to construct a polymer/manganese oxide layered structure

A layered nanocomposite with poly(diallyldimethylammonium), PDDA, intercalated between manganese oxide layers can be formed on a platinum electrode in a thin film form through a direct electrochemical route. The process involves a potentiostatic oxidation of aqueous Mn(2+) precursors in the presence of PDDA by applying a constant potential (+1.0 V vs Ag/AgCl).     

Characterization of preformed plasmas with an interferometer for ultra-short high-intensity laser-plasma interactions

The evolution of an Al preformed plasma produced by a prepulse was observed before and after the arrival of the main pulse by an interferometer using a femtosecond probe pulse. A central density depression due to the ponderomotive force of the main laser pulse in the preformed plasma with a 100 m scale length was clearly visible after the main pulse irradiation at an intensity of 5×10¹⁶ W/cm². The temporal profiles of the prepulse, characterized by a cross-correlation in conjunction with a precise density profile measurement by an interferometer, contribute to the better understanding of femtosecond laser-matter interactions. PACS 52.38.-r; 52.50.Jm; 52.70.-m     

The first example of alpha-thiomagnesiums generated from dithioacetal monoxides with Grignard reagent; their properties and some synthetic applications

Dithioacetal monoxides were synthesized from aldehydes and cyclohexanone, and reaction of the dithioacetal monoxides with Grignard reagents was investigated. The dithioacetal monoxide synthesized from alkylaldehyde and 4-chlorobenzenethiol reacted with i-PrMgCl to afford the desired alpha-thiomagnesium in high yield. The generated alpha-thiomagnesium was found to be stable at room temperature and to be useful in organic synthesis. In contrast to this, the dithioacetal monoxides derived from benzaldehyde and cyclohexanone did not give satisfactory results.     

Total synthesis of (+/-)-alpha- and beta-lycoranes by sequential chemoselective conjugate addition-stereoselective nitro-Michael cyclization of an omega-nitro-alpha,beta,psi,omega-unsaturated ester

[reaction: see text] An omega-nitro-alpha,beta,psi,omega-unsaturated ester underwent a chemoselective conjugate addition of a nitroolefin moiety with aryllithium to produce a psi-aryl-omega-nitro-alpha,beta-unsaturated ester, which was then stereoselectively cyclized by intramolecular nitro-Michael reaction giving a functionalized cyclohexane applicable to the total synthesis of (+/-)-alpha- and beta-lycoranes.     

Rapid Separation of Hydrophobic Compounds by UPLC: in Case of Bisindolylmaleimides, Indolocarbazoles or Fullerene C60 Derivatives

Rapid separation of hydrophobic compounds such as bisindolylmaleimides, indolocarbazoles or fullerene C₆₀ derivatives by ultra performance liquid chromatography was developed. Bisindolylmaleimides and indolocarbazoles were separated within 7 and 5 min, respectively. The linear ranges for the determination of bisindolylmaleimides and indolocarbazoles were 1.25?500 pmol and 0.5?50 pmol per injection (r > 0.99), respectively. Fullerene C₆₀ derivatives were separated within 9 min, and the linear range for the determination of fullerene C₆₀ derivatives was 0.1?10 pmol per injection (r > 0.99).     

Optimization of asymmetric hydrogenation of 3-phenyl-3-butenoic acid catalyzed by rhodium(I)-4,5-bis[(diphenylphosphino)methyl]-2,2-dimethyldioxolane (DIOP)

Enantioselective, homogeneous hydrogenation of 3-phenyl-3-butenoic acid (1) has extensively been examined in the presence of the rhodium(I)/4,5-bis[(diphenylphosphino)methyl]-2,2-dimethyldioxolane (DIOP) catalyst systems. Optimization of the reaction conditions was undertaken mainly by controlling effects of added tertiary amines as well as solvent polarities on the enantio-selectivity of the product. The best asymmetric yield (85.1% e.e.) was attained when the hydrogenation was carried out in the presence of triethylamine (5 mol%) in 75% aqueous methanol using a neutral rhodium-DIOP catalyst.