Density functional study of the l-proline-catalyzed α-aminoxylation of aldehydes reaction: The reaction mechanism and selectivity

The reaction mechanism of the l-proline-catalyzed α-aminoxylation reaction between aldehyde and nitrosobenzene has been investigated using density functional theory (DFT) calculation. Our calculation results reveal following conclusions [1]. The first step that corresponds to the formation of C–O bond, is the stereocontrolling and rate-determining step [2]. Among four reaction channels, the syn-attack reaction channel is more favorable than that of the anti one, and the TS-ss channel dominates among the four channels for this reaction in the step of C–O bond formation [3]. The intermolecular hydrogen bond between the acidic hydrogen of l-proline and the N atom of the nitrosobenzene in an early stage of the process catalyzes very effectively the C–O bond formation by a large stabilization of the negative charge that is developing at the O atom along the electrophilic attack [4]. The effect of solvent decreases the activation energy, and also, the calculated energy barriers are decrease with the enhancement of dielectric constants for C–O bond formation step. These results are in good agreement with experiment, and allow us to explain the origin of the catalysis and stereoselectivity for l-proline-catalyzed α-aminoxylation of aldehyde reaction. The addition of H₂O to substituted imine proline, intermolecular proton-transfer steps, and the l-proline elimination process were also studied in this paper.     

Some inequalities for partial orders

We establish some inequalities connecting natural parameters of a partial order P. For example, if every interval [a,b] contains at most maximal chains, if some antichain has cardinality v, and if there are ₁ chains whose union is cofinal and coinitial in P, then the chain decomposition number for P is ₁v (Theorem 2.2), and the inequality is sharp in a certain sense (Section 3).This paper was written while the authors were visitors at the Laboratoire d'algèbre ordinale, Département de Mathématiques, Université Claude Bernard, Lyon 1, France.Research supported by NSERC grant # A5198.     

Effects of surface nonlinear interactions on the local critical behavior

The energy spectrum and the wave functions of quantum wells in strong magnetic fields parallel to the potential walls are calculated analytically by means of a new, graph supported method. This Arrow Train Method allows to solve the recurrence relations which originate in the evaluation of eigenvalue determinants of infinite order. The energy eigenvalues for infinite barrier height are computed as a power series in the magnetic fieldB and the center of orbit coordinatez ₀. The power series is evaluated up to the 18th order inB ² for the first four levels and for cyclotron radii comparable to or considerable less than the well width. The corresponding wave functions and the field dependent center of mass shifts are obtained.Work supported in part by the Deutsche Forschungsgemeinschaft     

Cluster model study of lightp-shell Λ-hypernuclei with OBE-based effective ΛN interaction

The structures of the lightp-shell hypernuclei \({}_\Lambda ^6 He,{}_\Lambda ^7 Li,{}_\Lambda ^9 Liand{}_\Lambda ^9 Be\) are studied by using a realistic effectiveΛN interaction (YNG), and compared to those with the use of the simple one-range Gaussian (ORG) interaction. The YNG interaction, which simulates theΛNG-matrix for the Nijmegen OBE modelD, is characterized by the inner repulsive core and the density-dependence along with the space-exchange and spin-spin components. The framework we adopt is the microscopic α +x + Λ (x=n, d, t or α) three-cluster model, where nucleon antisymmetrization is exactly treated. The characteristic behaviors ofΛ?x andΛ?(αx) interactions derived from the YNG are displayed and discussed. In spite of the remarkable characteristic of YNG, the calculated energy levels of the four hypernuclei are very similar to those previous obtained by using the simple ORG interaction. The stabilization and contraction of the hypernuclear system due to the glue-like role ofΛ-particle persists in the present calculation, though the repulsive core of theΛN interaction tends to prevent from too much contraction.     

The global topological meaning of cocycles in a Gauge group

This Letter shows explicitly that the descent sequence of cocycles in a gauge group realizes the ech-de Rham double complex. Meanwhile the ech complex corresponds to finite gauge transformations. This Letter also shows how the indices of each order of cocycles characterizes the obstructions on overlapping spheres in different dimensions and how these indices are equal to a common one.     

Optical frequency doubling of a single-mode dye laser in an external ring resonator

Optical frequency doubling of a single-mode cw Rhodamin 6G ring dye laser is performed with a thin angle-tuned LiIO₃ Brewster cut crystal in a stabilized passive ring resonator. A conversion efficiency of =5 mW uv/320 mW fundamental input power was achieved at =603 nm.     

Odd/even effect in the chain length on the enthalpy of micellization of gemini surfactants in aqueous solution

The micellization properties of cationic symmetric gemini surfactants, [CmH(2m+1)(CH3)2N(CH2)6N(CH3)2CmH(2m+1)]Br2 (designated as CmC6CmBr2, with m = 7, 8, 9, 10, 11, 12, and 16), has been investigated by isothermal titration microcalorimetry. The critical micelle concentration (CMC) and enthalpy of micellization (DeltaHmic) were determined from calorimetric titration curves. The linear decreasing of log CMC with increasing the length of the hydrophobic chain is consistent with an increase in the hydrophobicity of the alkyl chain. Interestingly, with increasing the length of the alkyl chain, the DeltaHmic values of the surfactants with even numbered alkyl chains vary from endothermic to exothermic, whereas the DeltaHmic values of the surfactants with odd numbered alkyl chains are all endothermic and tend to become more endothermic. The pronounced even/odd effect in DeltaHmic is discussed with respect to the "donor-acceptor" interaction.     

3'-nitrophenylpropyloxycarbonyl (NPPOC) protecting groups for high-fidelity automated 5' --> 3' photochemical DNA synthesis

[structure: see text]. The most powerful DNA microarrays would be prepared by photolithography with free 3'-ends that could be processed enzymatically. A photoremovable group that could be removed in quantitative yield would ensure high purity of the synthesized probes. We have developed new pyrimidine building blocks for 5' --> 3' DNA synthesis with high cycle yields using the NPPOC (3'-nitrophenylpropyloxycarbonyl) protecting group. These phosphoramidites were proved in automated photochemical DNA synthesis on a modified synthesizer.