Lewis acid-catalyzed asymmetric hydroxymethylation of silicon enolates in aqueous media

Asymmetric hydroxymethylation of silicon enolates with formaldehyde in aqueous media has been achieved using praseodymium triflate and a chiral crown ether. Formaldehyde aqueous solution can be directly used for the reactions, and a water/THF mixture was found to be the best solvent system. This is the first example of catalytic asymmetric hydroxymethylation of silicon enolates.     

Bis(2-bromoethyl) selenium dibromide as the selenium-introducing reagent: One-pot preparation of 2,5-bis(alkoxymethyl)tetrahydroselenophenes by the cyclization of 1,5-hexadiene

The reaction of bis(2-bromoethyl)selenium dibromide (1a) with 1,5-hexadiene (2) in methanol or ethanol affords 2,5-bis(alkoxymethyl)tetrahydroselenophene-1,1-dibromides (R = CH₃ (3b), R = C₂H₅ (3c)) via 2,5-bis(bromomethyl)tetrahydroselenophene-1,1-dibromide (3a). The reaction of 1a with 2 in 1-propanol, 2-methyl-1-propanol or 1-butanol in the presence of sodium carbonate gave 2,5-bis(alkoxymethyl)tetrahydroselenophene (R = C₃H₇ (4a), R = (CH₃)₂CHCH₂ (4b) and R = C₄H₉ (4c)) via 3a. The ratios of the trans and cis isomers of 3a–3c are 3:2. In addition, the structure of trans-2,5-bis(methoxymethyl)tetrahydroselenophene-1,1-dibromide (trans-3b) was determined by X-ray crystallography.     

Remote asymmetric induction with vinylketene silyl n,o-acetal

A highly regio- and diastereoselective TiCl4-mediated vinylogous Mukaiyama aldol reaction using the chiral vinylketene silyl N,O-acetal has been developed. The present vinylogous Mukaiyama aldol reaction provides a unique and effective means of controlling remote asymmetric induction. The methyl group at the alpha-position is important in achieving a high level of stereoselectivity. From a synthetic point of view, this methodology can provide a one-step construction of delta-hydroxy-alpha,gamma-dimethyl-alpha,beta-unsaturated carbonyl unit that is seen in many natural polyketide products.     

Superconductivity and crystallographic properties of La2 − xMxCuO4 − δ (M = Na, K)

Superconductivity and crystallographic properties of La_{2 − x}M_xCuO_{4 − δ} (M = Na, K) are studied. In the La_{2 − x}M_xCuO_{4 − δ} system, superconductivity is detected for x 0.2. Oxygen content analysis shows that the system has more oxygen vacancies than the La_{2 − x}Sr_xCuO_{4 − δ} system. These oxygen vacancies may reduce the hole concentration, and high Na-doping is needed to produce superconductivity. In the La_{2 − x}K_xCuO_{4 − δ} system, superconductivity is observed for the first time. Resistivity and magnetic susceptibility measurements show that T_c(onset) is 40 K and the Meissner volume fraction is about 4% for x = 0.7. The system changes from orthorhombic to a tetragonal K₂NiF₄ structure at x ≈ 0.3 and only tetragonal samples show superconductivity.     

Synthesis of Twisted [n]Cycloparaphenylene by Alkene Insertion

Mono-alkene-inserted [n]cycloparaphenylenes 1 [(ene)-[n]CPP] with n=6, 8, and 10, mono-ortho-phenylene-inserted [6]CPP 2 , and di-alkene-insertved [n]CPP 3 [(ene)₂-[n]CPP] with n=4, 6, and 8 were synthesized by fusing CPP precursors and alkene or ortho- phenylene groups through coupling reactions. Single-crystal X-ray diffraction analyses reveal that the strips formed by the π-surfaces of 1 and 2 exhibited a Möbius topology in the solid state. While the Möbius topology in the parent 1 and 2 in solution was lost due to the free rotation of the paraphenylene unit even at low temperatures, ene-[6]CPP 4 with eight 1-pyrrolyl groups preserved the Möbius topology even in solution. Despite a twist, 1 has in-plane conjugation and possesses a unique size dependence of the electronic properties: namely, the opposite size dependency of the HOMO–LUMO energy relative to conventional π-conjugated molecules.     

Chiral Dinuclear EuIII,TbIII, and YIII Complexes Supported by P-Stereogenic Linear Tetraphosphine Tetraoxide

A P-stereogenic linear tetraphosphine tetraoxide, (R,R)- or (S,S)-dpmppm(=O)₄, was synthesized to prepare C₂ dinuclear M(hfa)₃ complexes (M=Eu, Tb, Y) as the first example of lanthanide(III) complexes with P-chiral multidentate phosphine oxides. The mononuclear M(hfa)₃ complexes (M=Eu, Y) with a P-chiral diphosphine dioxide, tpdpb(=O)₂, were also prepared, and comparison of their photophysical properties for the Eu^III complexes revealed that significant chiral induction from the P-chiral centers arises on the achiral M(hfa)₃ units through intramolecular π-π stacking constraint in the dinuclear system.     

Direct numerical simulation of elastic turbulence and its mixing-enhancement effect in a straight channel flow

In this paper,we present a direct numerical simulation(DNS) of elastic turbulence of viscoelastic fluid at vanishingly low Reynolds number(Re = 1) in a three-dimensional straight channel flow for the first time,using the Giesekus constitutive model for the fluid.In order to generate and maintain the turbulent fluid motion in the straight channel,a sinusoidal force term is added to the momentum equation,and then the elastic turbulence is numerically realized with an initialized chaotic velocity field and a stretched conformation field.Statistical and structural characteristics of the elastic turbulence therein are analyzed based on the detailed information obtained from the DNS.The fluid mixing enhancement effect of elastic turbulence is also demonstrated for the potential applications of this phenomenon.     

Calculation of heat transfer and uniformity of chemical amplification during post-exposure bake

Heat transfer in a resist-coated silicon wafer using a bake process is theoretically evaluated by modeling the three-dimensional diffusion process, focusing on the controllability of the lithographic performance of chemically amplified resists. Six models of various ambient conditions are used. The proximity gap between the hotplate and the wafer is found to have a dominant influence on the heat transfer process for the whole system. Because the atmosphere near the wafer acts as a thermal diffusion buffer layer, no temperature gradient occurs in the resist, even when it is subjected to convective heat transfer from the resist surface. Experimental results obtained by X-ray lithography confirm the calculation results.