Highly Selective Asymmetric Intramolecular Selenocyclisation

Asymmetric intramolecular selenocyclisation of alkenoic acids, alkenols and alkenyl urethanes using chiral ferrocenylselenenyl cations proceeds smoothly to give the corresponding lactones, cyclic ethers and N-heterocyclic compounds, respectively, in moderate yields with very high diastereoselectivities.     

Chiral Bis(oxazoline)-copper Catalyzed Enantioselective Imidation of Sulfides

Prochiral sulfides reacted with Phl=NTs in the presence of a catalytic amount of Cu(I) salt together with a chiral 4,4′-disubstituted bis(oxazoline) ligand to afford the corresponding chiral sulfimides.     

REACTION OF SULFUR CHLORIDE WITH ACETOPHENONE. II

Abstract

In a previous paper,¹ we reported the formation of a resinous material (1) from the reaction of sulfur chloride with acetophenone which, upon treatment with DMF, yielded phenylglyoxylthiodimethylamide (4). We now report two additional resinous materials (5, 6), resulting from bromination of sodium phenacylthiosulfate (3) and diphenacyl disulfide (7) respectively, both of which not only resemble resinous 1 in appearance, but also yield 4 upon treatment with DMF in aqueous alkali.

Resinous 1, 5, and 6 appear to have the same common basic structure and differ only in the number of sulfur atoms bonded between the common units. Cleavage at the sulfur-sulfur bonds and elimination of hydrogen halide then yields identical oxothioamides from 1, 5, or 6. The latter appears to be a general reaction, and several oxothioamides were prepared by this synthetic method from 1, 5, and 6 and various amides and amines.     

Chalcogen Chiral Ylides for the Catalytic Asymmetric Epoxidation of Aldehydes: From Sulfur to Selenium and Tellurium

Abstract

The reaction of novel chiral selenonium and telluronium ylides was investigated with aldehydes and compared to the sulfur analogues. (2R,5R)-2,5-Dimethylselenolane was prepared and reacted as a catalyst for the benzylidenation of aldehydes. Disubstituted epoxides were readily prepared with a (surprising) absence of diastereoselectivity, and with enantiomeric excesses higher than 90%. The reaction of a tellurium analogue, (2S,5S)-2,5-diethyltellurolane, afforded the oxirane in very moderate yield and e.e.'s in the range of 62–82%. Though this was less productive, it is the first report of a chiral telluronium ylide leading to an asymmetric epoxidation of aldehydes.     

Magnetic properties of La-Co substituted M-type strontium hexaferrites prepared by polymerizable complex method

Magnetic properties of La-Co substituted M-type strontium hexaferrites were studied. The samples were prepared by polymerizable complex method. Crystal structure of samples has been investigated by powder X-ray diffraction (XRD). Single-phase M-type strontium hexaferrites with chemical composition of Sr_1.05−xLa_xFe_12−xCo_xO₁₉ (x=0-0.4) were formed by heating at 1173 K for 24 h in air. Magnetic properties were discussed by measurements of M-H curves with vibrating sample magnetometer (VSM). La-Co substituted M-type strontium hexaferrites prepared by polymerizable complex method showed typical magnetic hysteresis of hard ferrite. The coercive force increased significantly by La-Co substitution with polymerizable complex method. Maximum coercive force achieved in this study is 8.0 kOe (640 kA/m). Scanning electron microscopy revealed that the prepared ferrite particles have plate-like shape of diameter range between 20 and 500 nm.     

Stein's positive part estimator and bayes estimator

Summary Stein's positive part estimator forp normal means is known to dominate the M.L.E. ifp≧3. In this article by introducing some proirs we show that Stein's positive part estimator is posterior mode. We also consider the Bayes estimators (posterior mean) with respect to the same priors and show that some of them dominate M.L.E. and are admissible.     

Ab initio molecular orbital calculations of the cobalt porphine complex. I. LCAO SCF MO calculation of low-spin,high-spin,and π-ionized states of Co-porphine

Ab initio LCAO SCF MO calculations are carried out on planar Co-porphine with a basis set of roughly double zeta quality for Co and N and of single zeta quality for C and H. The net charge on Co and N and the overlap population between them are 1.78, ?0.57, and 0.06, respectively, in the ²A_1g, state, which is known to be the ground state by experiment. The bonding in this complex is thus largely ionic. The first and second calculated ionization potentials are 6.51 and 6.77 eV, respectively, and are in reasonable agreement with the observed ionization potentials of 6.44 and 6.62 eV for Ni-tetraphenylporphine. CI calculations within the framework of the ligand field theory are also performed. The calculated order of the five lowest states is ⁴B_2g ≈ ⁴E_g, ⁴A_2g, ²A_1g, ⁴E_g from below and is not in agreement with the semiempirical order of ²A_1g ≈ ⁴B_2G, ⁴A_2g, ²E_g, ⁴E_g determined by Lin.     

Amination of ethers using chloramine-T hydrate and a copper(I) catalyst

Amination of C-H bonds activated by ether oxygen atoms is facile with chloramine-T as nitrene source and copper(I) chloride in acetonitrile as catalyst. For cyclic ethers the hemiaminal products are generally stable and can be isolated pure. For acyclic ethers, the hemiaminal products, as expected, fragment with elimination of alcohol to yield imines. When activation of benzylic positions is remote through a conjugated system, stable benzylamine derivatives are isolated. Mechanistic studies are consistent with concerted insertion of an electrophilic nitrenoid into the C-H bond in the rate-determining step, though in an asynchronous manner with a more activated substrate.     

Preparation of sterically congested di(4-pyridyl)diazomethanes and characterization of triplet carbenes from them

Di(4-pyridyl)diazomethanes having two and four ortho chlorine groups were prepared, and the triplet carbenes generated from them were characterized by ESR and UV/vis at low temperature and time-resolved UV/vis at room temperature. An appreciable increase in the stability of triplet carbenes is achieved by introducing ortho chlorine groups. [structure: see text]