Kinetic resolution displaying zeroth order dependence on substrate consumption: copper-catalyzed asymmetric alcoholysis of azlactones

Kinetic resolution of 4-alkyl-2-aryl-5-oxo-4,5-dihydrooxazole-4-carboxylic acid esters (azlactones 1) were achieved by copper-DTBM-SEGPHOS catalyzed alcoholysis reaction with good selectivity (12 examples). Variation of ee of unreacted substrates 1 and products 2 with conversion was found to follow the theoretical line of zeroth-order kinetic resolution, for which the selectivity profiles and graphical analysis were presented for the first time. The efficiency of resolution in zeroth-order reaction is higher than first-order reaction. For example, the reaction with 1a afforded (S)-1a (99% ee) and (R)-2a (74% ee) at 57% conversion, where the k(rel) values were calculated to be 6.7 as zeroth-order kinetic resolution and 37 as first-order kinetic resolution.     

Collinear to spiral spin transformation without changing the modulation wavelength upon ferroelectric transition in Tb1-xDyxMnO3

Lattice modulation and magnetic structures in magnetoelectric compounds Tb1-xDyxMnO3 have been studied around the ferroelectric (FE) Curie temperature TC by x-ray and neutron diffraction. Temperature-independent modulation vectors through TC are observed for the compounds with 0.50 相似文献   

ORIENTATION OF RETINYLIDENE CHROMOPHORE OF HYPSORHODOPSIN IN FROG RETINA

Abstract— Hypsorhodopsin and bathorhodopsin were formed in the frog retina by irradiating rhodopsin at liquid He temperature (9 K) with orange light (> 520 nm) and blue light (437 nm), respectively. Hypsorhodopsin was converted to bathorhodopsin in the retina by warming above 32 K in the dark. Similar phenomena were observed in the rod outer segment suspension. A difference spectrum between hypsorhodopsin and bathorhodopsin in the retina produced by warming was almost identical with that in the rod outer segment suspension. This suggests that the transition dipole moment of hypsorhodopsin is parallel to the disk membrane plane which is also parallel to that of bathorhodopsin.     

Highly Active Second-Order Nonlinearity from Sol-Gel Processed Poled Silica and Germanosilicate Thin Film

Poled silica and germanosilicate thin films are prepared with typical sol-gel processing. Second-order nonlinearity about one order of magnitude larger than that of quartz crystal is realized. Substrate effect and dopant effect on the nonlinearity are discussed.     

Current oscillation and low-field colossal magnetoresistance effect in phase-separated manganites

Current-induced switching from a metallic to an insulating state is observed in phase-separated states of (La(1-y)Pr(y))0.7Ca0.3MnO3 (y=0.7) and Nd(0.5)Ca(0.5)Mn(1-z)Cr(z)O3 (z=0.03) crystals. The application of magnetic fields to this current-induced insulating state causes a pronounced low-field negative magnetoresistance effect [rho(H)/rho(0)=10(-3) at H=1 kOe]. The application of a constant voltage also causes the breakdown of the Ohmic relation above a threshold voltage. At voltages higher than this threshold value, oscillations in currents are observed. This oscillation is well reproduced by a simple model of local switching of a percolative conduction path.     

Dihedral coverings of algebraic surfaces and their application

In this article, we study dihedral coverings of algebraic surfaces branched along curves with at most simple singularities. A criterion for a reduced curve to be the branch locus of some dihedral covering is given. As an application we have the following:

Let be a reduced plane curve of even degree having only nodes and cusps. If 2d^2 - 6d + 6$">, then is non-abelian.

Note that Nori's result implies that is abelian, provided that .

     

Hydrolysis of alkenyl esters and ethers catalyzed by metal complexes

[reaction: see text] Various kinds of transition metals catalyzed the hydrolysis of alkenyl esters and ethers under buffer-free, high concentration conditions compared to usual biocatalysts. Hydrolytic kinetic resolution of cis-2-tert-butylcyclohexyl vinyl ether was achieved by chiral (salen)Co complexes with good selectivity (k(rel) = 10.0).     

S‐((Phenylsulfonyl)difluoromethyl)thiophenium Salts: Carbon‐Selective Electrophilic Difluoromethylation of β‐Ketoesters, β‐Diketones,and Dicyanoalkylidenes

S‐((Phenylsulfonyl)difluoromethyl)thiophenium salts were designed and prepared by a triflic acid catalyzed intramolecular cyclization of ortho‐ethynyl aryldifluoromethyl sulfanes. The thiophenium salts were found to be efficient as electrophilic difluoromehtylating reagents for introduction of a CF₂H group to sp³‐hybridized carbon nucleophiles such as of β‐ketoesters and dicyanoalkylidenes. The (phenylsulfonyl)difluoromethyl group can be readily transformed into CF₂H under mild reaction conditions. Enantioselective electrophilic difluoromethylation was also achieved in the presence of bis(cinchona) alkaloids.     

Magnetic-field induced competition of two multiferroic orders in a triangular-lattice helimagnet MnI2

Magnetic and dielectric properties with varying magnitude and direction of magnetic-field H have been investigated for a triangular-lattice helimagnet MnI_{2}. The in-plane electric polarization P emerges in the proper screw magnetic ground state below 3.5 K, showing the rearrangement of six possible multiferroic domains as controlled by the in-plane H. With every 60° rotation of H around the [001] axis, discontinuous 120° flop of the P vector is observed as a result of the flop of magnetic modulation vector q. With increasing the in-plane H above 3 T, however, the stable q direction changes from q‖(110[ ˉover 0]) to q‖(110), leading to a change of P-flop patterns under rotating H. At the critical field region (～3 T), due to the phase competition and resultant enhanced q flexibility, the P vector smoothly rotates clockwise twice while the H vector rotates counterclockwise once.     

Synthesis of Both Enantiomers of Nine‐Membered CF3‐Substituted Heterocycles Using a Single Chiral Ligand: Palladium‐Catalyzed Decarboxylative Ring Expansion with Kinetic Resolution

The two enantiomers of trifluoromethyl‐benzo[c][1,5]oxazonines, (R)‐ 4 and (S)‐ 4 , can be selectively accessed with high enantiopurity by the Pd‐catalyzed ring‐expansion reaction of trifluoromethyl‐benzo[d][1,3]oxazinones ( 1 ) with vinyl ethylene carbonates ( 3 ) using one antipode of a chiral ligand. Initially, the reaction proceeds by a double decarboxylative ring‐expansion with kinetic resolution of 1 in the presence of a Pd‐catalyst/chiral ligand to provide (R)‐ 4 with high enantiopurity. At the same time, the nonreactive antipode of 1 , (S)‐ 1 , which was recovered with an impeccable s factor of up to 713 and an ideal chemical yield, was transferred into the antipode of the products, (S)‐ 4 , with high enantiopurity by a second run of the Pd‐catalyzed double decarboxylation reaction, but this time without any chiral auxiliary. Thus, both antipodes of the chiral trifluoromethyl heterocycles 4 can be obtained in excellent enantiopurity using only a single antipode of the chiral catalyst.