SmI2-promoted tandem desulfurization and reductive coupling reactions of aromatic lactams with carbonyl compounds

Treatment of sulfur-substituted aromatic lactams with carbonyl compounds in the presence of samarium(II) diiodide was found to undergo novel tandem desulfurization and reductive coupling reactions to generate -hydroxyalkylated lactams in high yield. Stereochemistry of the coupling products was researched and the results that decreasing the steric bulkiness of the N-substituents as well as raising the reaction temperature leads to an increase of the erythro-selectivity were observed. The mechanistic origins of this stereoselectivity are also briefly documented.     

Quantitative analysis of organic additive content in a polymer by ToF-SIMS with PCA

Quantitative analysis of organic materials by ToF-SIMS is intrinsically difficult because of their tendency to decompose under ion irradiation. In this study, we applied principal component analysis (PCA) as a means of compensation for the spectral degradation caused by this decomposition and thus improve the accuracy of the quantitative analysis, using as models two organic additives of quite different composition and vulnerability to decomposition under ion irradiation, in polystyrene. This enables the extraction of a principal component related to their content that is independent of the decomposition. The effectiveness of this approach in quantitative analysis of organic additives content in polymers without loss in accuracy due to spectral degradation will be discussed.     

Dissipative crystallization of aqueous solutions of hydroxypropyl cellulose

Drying dissipative structures of aqueous solutions of hydroxypropyl cellulose, their viscosities of 2 wt.% solutions ranging from 2 to 2,000 mPa.s were studied on a cover glass, a watch glass, and a Petri glass dish. The thickness profile of the dried film shows the coexistence of a low round hill and a high broad ring on a cover glass. The broad ring size increased as molecular weight and/or concentration of the polymers increased on a cover glass and a watch glass. Microscopic drying crystal patterns of HPC changed as a function of the distance from the film center, which is one of the typical results of the dissipative crystallization. Rod-like microscopic drying patterns originated in the cholesteric liquid crystalline structures were observed. The rods oriented mainly parallel and in some case perpendicularly to the radial direction of the dried film except the central area, where the rods distributed at random. These orientation effects were significant for low molecular weight samples and in a watch glass.     

Dissipative crystallization of sodium salt of deoxyribonucleic acid

Drying patterns of aqueous solutions of sodium salt of deoxyribonucleic acid (NaDNA) were studied on a cover glass, a watch glass, and a Petri glass dish at room temperature. Orientation of the rod-like single crystals of NaDNA molecules in the radial direction was observed especially at low polymer concentrations. The ratios of the size of the broad ring against initial size of the liquid on a cover glass and a watch glass were very small between 0.05 and 0.1 compared with those of the typical polyelectrolytes. Main cause is the compact conformation of NaDNA forming single or double stranded helix structures in the dried film. Microscopic drying patterns were long rods accompanied with the many short rods especially on a cover glass. Thick and short rods and dendritic crystals were fogrmed at the inward and outward areas of the dried films, respectively, on a watch glass and a Petri glass dish. Rod-like and dendritic crystals resembled the distorted hedrite and/or spherulite structures. Dissipative crystallization such as the orientation and accumulation of the single crystals of NaDNA were observed and the importance of the convectional and sedimentation processes was demonstrated during the course of crystallization.     

Inverse electron demand asymmetric cycloadditions of cyclic carbonyl ylides catalyzed by chiral Lewis acids—Scope and limitations of diazo and olefinic substrates

High enantioselectivities (94-96% ee) were obtained for the inverse electron-demand 1,3-dipolar cycloadditions between cyclohexyl vinyl ether and 2-benzopyrylium-4-olate generated via Rh₂(OAc)₄-catalyzed decomposition of o-methoxycarbonyl-α-diazoacetophenone. The reactions were effectively catalyzed by Eu(OTf)₃, Ho(OTf)₃, or Gd(OTf)₃ complexes (10 mol %) of chiral 2,6-bis[(4S,5S)-4,5-diphenyl-2-oxazolinyl]pyridine. The reactions with the other electron-rich dipolarophiles such as allyl alcohol, 2,3-dihydrofuran, and butyl-tert-butyldimethylsilylketene acetal showed moderate enanantioselectivities (60-73% ee). Good to high enantioselectivities (73-97% ee) were also obtained for the cycloadditions between 3-acyl-2-benzopyrylium-4-olates, generated from methyl 2-(2-diazo-1,3-dioxoalkyl)benzoates and butyl or cyclohexyl vinyl ethers, in the presence of binaphthyldiimine (BINIM)-Ni(II) complexes (10 mol %). Under similar conditions, the reaction between methyl 2-(2-diazo-1,3-dioxohexyl)benzoate and 2,3-dihydrofuran was highly endo-selective, and moderately enantioselective (70% ee). For the BINIM-Ni(II)-catalyzed reactions of cyclohexyl vinyl ether, the use of an epoxyindanone as the 3-acyl-2-benzopyrylium-4-olate precursor revealed that the chiral Lewis acid can function as a catalyst for asymmetric induction. The scope of the cyclic carbonyl ylides was extended to those generated from 1-diazo-2,5-pentanedione derivatives, which were reacted with butyl or TBS vinyl ether and catalyzed using the (4S,5S)-Pybox-4,5-Ph₂-Lu(OTf)₃ complex to give good levels of asymmetric inductions (75-84% ee).     

Novel biphasic reaction system of ferric chloride dissolved imidazolium hexafluorophosphate and benzotrifluoride: application to electron transfer reaction of cyclopropyl silyl ethers

Ferric chloride (FeCl₃) promoted electron transfer oxidation of bicyclic cyclopropyl silyl ethers was performed in biphasic solution system of 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF₆) and benzotrifluoride (BTF). The resulting chloro-substituted ring-expanded cycloalkanones were treated with an appropriate base to produce substituted cyclic enones. These two-step reactions were successfully devised to proceed in a simpler manner in which the ordinary work-up operations for the former oxidation step, such as water-quench, extraction, and evaporation, were omitted; imidazole was found to be the most suitable base for the latter elimination step.     

Theoretical study on quantum dynamics of bose system interacting with photon field

We investigate the quantum dynamics of two‐boson and two‐level systems interacting with a one‐mode photon field. The time evolution of the population for each state is calculated in terms of the Jaynes–Cummings model. We find the collapses and revivals of the order parameter for the Bose–Einstein condensation. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem 84: 401–408, 2001     

Microcalorimetry investigation of synthetic hemoprotein (albumin‐heme)

Recombinant human serum albumin (rHSA) incorporating the iron(II) complex of the tetraphenylporphyrin derivative (FepivP or FecycP) is a synthetic O₂‐carrying hemoprotein [albumin‐heme (rHSA‐FepivP or rHSA‐FecycP)], which acts as a red blood cell substitute. The association and dissociation behavior of FepivP and FecycP with rHSA has been initially investigated by isothermal titration calorimetry. A strong heat release appeared after the injection of albumin‐heme into a large molar excess of rHSA. This exothermic enthalpy change was due to the transference of hemes to the other free albumins. The difference in the heme binding affinity to rHSA can be manifested in the enthalpy term. Copyright © 2003 John Wiley & Sons, Ltd.