Enantioselective O- and N-nitroso aldol synthesis of tin enolates. Isolation of three BINAP-silver complexes and their role in regio- and enantioselectivity

The selective generation of three different silver-BINAP catalysts has been achieved via the proper combination of metal/ligand ratio and/or choice of silver salt. Indeed, the X-ray crystallographic study has been used to gain insight into the structure of the catalyst. After the evaluation of each species, 1:1 (AgX.(R)-BINAP) complex was found to be the real active species in the O-selective nitroso aldol reaction. On the other hand, a systematic survey of solvent has shown that the optimal 2:1 (AgX.(R)-BINAP) complex is the effective catalyst in the N-selective pathway. Thus, a new method of generation of the silver-BINAP catalyst and the synthetic transformations provide not only new insights into the developing area of catalytic enantioselective nitroso aldol synthesis but also clear guidance for the design of an effective catalyst.     

Remarkable tris(trimethylsilyl)silyl group for diastereoselective [2 + 2] cyclizations

[reaction: see text] Diastereoselective [2 + 2] cyclizations of aldehyde- and ketone-derived silyl enol ethers with acrylates is described. The use of the tris(trimethylsilyl)silyl group allows for unprecedented reactivity, yields, and selectivity for these cyclizations. The presence of silicon-silicon bonds proved to be important for this transformation, where typical silyl groups (TBS and TIPS) failed to give any desired product. The bulky bis(2,6-diphenylphenoxide) aluminum triflimide catalyst was essential for high diastereoselectivity.     

Reaction of poly(vinyl chloride) with magnesium and grignard reagents

Reaction of poly(vinyl chloride) with magnesium under various conditions was attempted, but poly(vinyl chloride) did not react with magnesium. The reactions of poly(vinyl chloride) with benzylmagnesium chloride and allylmagnesium chloride as Grignard reagents were carried out in tetrahydrofuran at reflux temperature. It was found that the chlorine atoms in the poly(vinyl chloride) were replaced by benzyl and allyl groups by the coupling reaction, and a small amount of Grignard reagent of poly(vinyl chloride) was formed by the magnesium–halogen exchange reaction. The extent of the substitution increased with increasing reaction time and concentration of the Grignard reagent.     

An economical approach for peptide synthesis via regioselective C–N bond cleavage of lactams

An economical, solvent-free, and metal-free method for peptide synthesis via C–N bond cleavage using lactams has been developed. The method not only eliminates the need for condensation agents and their auxiliaries, which are essential for conventional peptide synthesis, but also exhibits high atom economy. The reaction is versatile because it can tolerate side chains bearing a range of functional groups, affording up to >99% yields of the corresponding peptides without racemisation or polymerisation. Moreover, the developed strategy enables peptide segment coupling, providing access to a hexapeptide that occurs as a repeat sequence in spider silk proteins.

An economical, solvent-free, and metal-free method for peptide synthesis via C–N bond cleavage using lactams has been developed.     

Application of 28Mg to the kinetic study of Mg uptake by rice plants

The time course of Mg uptake and release using intact rice plants and ²⁸Mg as a tracer is presented. Since there is no conventional Mg tracer available, ²⁸Mg was produced via ²⁷Al(α, 3p)²⁸Mg reaction using a cyclotron. Using the purified ²⁸Mg tracer, it was found that the uptake amount of ²⁸Mg by the rice plants increased linearly during 30 min of application. After ²⁸Mg treatment for 90 min, the roots were sequentially washed with iced solution for 120 min. Within about 10 min, almost all of the ²⁸Mg, that was thought to be weakly bound to the apoplast, was washed away.     

Optical-Optical Double Resonance Spectroscopy of the 1g(P1)-AΠ (1u)-XΣg Transition of I2

Optical-optical double resonance spectroscopy was used to study the 1_g(³P₁) ion-pair state of I₂ correlating to I⁻(¹S)+I⁺³P₁) at the dissociation limit. We gained access to the 1_g(³P₁) state though the A³Π (1_u) state in the (1+1) photon-excitation scheme. The pump laser excited the A³Π (1_u)-X¹Σ_g⁺ transition at a fixed frequency for state selection. The probe laser was scanned to detect the 1_g(³P₁)-A³Π (1_u) resonance by monitoring the ultraviolet emission from the 1_g(³P₁) state at 278 nm. The 1_g(³P₁) state was observed in a vibrational progression consisting of P and R doublets. An energy level analysis was carried out for the 1_g(³P₁) state in the 0≤ v ≤ 14 and 12≤J≤135 range, which led to a set of molecular parameters including the Ω-doubling constant. The Ω-doubling of the 1_g(³P₁) state was discussed by the pure precession model and interpreted to occur through the heterogeneous coupling with the 0_g⁻(³P₁) state correlating to the same ionic asymptote.     

Observation of the Fano-Kondo antiresonance in a quantum wire with a side-coupled quantum dot

We have observed the Fano-Kondo antiresonance in a quantum wire with a side-coupled quantum dot. In a weak coupling regime, dips due to the Fano effect appeared. As the coupling strength increased, conductance in the regions between the dips decreased alternately. From the temperature dependence and the response to the magnetic field, we conclude that the conductance reduction is due to the Fano-Kondo antiresonance. At a Kondo valley with the Fano parameter q approximately 0, the phase shift is locked to pi/2 against the gate voltage when the system is close to the unitary limit in agreement with theoretical predictions by Gerland et al. [Phys. Rev. Lett. 84, 3710 (2000)].     

Structure determination of the Cu(0 0 1)–c(4 × 4)-Sn surface by low-energy electron diffraction

Low-energy electron diffraction (LEED) have been used to determine the Cu(0 0 1)–c(4 × 4)-Sn structure formed at 300 K. It is demonstrated that a structural model suggested by scanning tunneling microscopy observations is correct: The model consists of one substitutional Sn atom and four Sn adatoms in the unit cell. Optimum parameters of the determined c(4 × 4) structure reveal that Sn adatoms laterally are displaced by 0.30 Å away from ideal fourfold-hollow sites along the 〈100〉 directions. It is proposed that such displacements of the Sn adatoms cause the formation of a network of octagonal rings on Cu(0 0 1). The substitutional Sn atom is located at each center of the octagonal rings. The formation conditions of the network are discussed.     

An energy-conserving Galerkin scheme for a class of nonlinear dispersive equations

A Galerkin scheme is presented for a class of conservative nonlinear dispersive equations, such as the Camassa–Holm equation and the regularized long wave equation. The scheme has two advantageous features: first, it is conservative in that it keeps the discrete analogue of the continuous energy conservation property in the original equations; second, it can be formulated only with cheap H¹$H^1$-elements even if the original equations include third derivative u_xxx$u_{\mathit{xxx}}$. Numerical experiments confirm the stability and effectiveness of the proposed scheme.