Catalytic Asymmetric Diels–Alder Reaction of Quinone Imine Ketals: A Site‐Divergent Approach

The catalytic asymmetric Diels–Alder reaction of quinone imine ketals with diene carbamates catalyzed by axially chiral dicarboxylic acids is reported herein. A variety of primary and secondary alkyl‐substituted quinone derivatives which have not been applied in previous asymmetric quinone Diels–Alder reactions could be employed using this method. More importantly, we succeeded in developing a strategy to divert the reaction site in unsymmetrical 3‐alkyl quinone imine ketals from the inherently favored unsubstituted C?C bond to the disfavored alkyl‐substituted C?C bond.     

Recyclable Ligands for the Non‐Enzymatic Dynamic Kinetic Resolution of Challenging α‐Amino Acids

Structurally simple and inexpensive chiral tridentate ligands were employed for substantially advancing the purely chemical dynamic kinetic resolution (DKR) of unprotected racemic tailor‐made α‐amino acids (TM‐α‐AAs), enabling the first DKR of TM‐α‐AAs bearing tertiary alkyl chains as well as multiple unprotected functional groups. Owing to the operationally convenient conditions, virtually complete stereoselectivity, and full recyclability of the source of chirality, this method should find wide applications for the preparation of TM‐α‐AAs, especially on large scale.     

Extension of a DNA molecule by local heating with a laser

Thermal convection and thermophoresis induced by mum-scale local heating are shown to elongate a single DNA molecule. An infrared laser used as a point heat source is converged into a dispersion solution of DNA molecules, which is observed under a fluorescent microscope. The thermal convection around the laser focus manifests as extensional flow for the long DNA chain. A simulation of thermal convection that reproduces the experimental condition provides numerical support for the stretching caused by thermal convection. This DNA elongation technique is a novel method for manipulating the intact single DNA molecules, and it can be applied to a "lab on a chip".     

Superfluidity of 4He in one and three dimensions realized in nanopores

Superfluidity in one and three dimensions has been studied for 4He fluid films adsorbed in nanopores which are straight channels and three-dimensionally connected pores, respectively. We observed the superfluid in one and three dimensions where thermal phonon wavelengths are much longer than the channel diameter and the period of the pore connection, respectively, and found that the superfluid onset depends on the pore connection. In the straight channels, the observed superfluid density disappears at a temperature far below the heat capacity anomaly of the Ginzburg-Landau transition, while in the pores connected in three dimension, the adsorbed 4He films show an evident three-dimensional transition where the superfluid onset occurs at the heat capacity peak.     

Ideal soft mode-type quantum phase transition and phase coexistence at quantum critical point in 18O-exchanged SrTiO3

The quantum ferroelectric phase transition of 18O-exchanged SrTiO3 (x% exchanged SrTiO3 is abbreviated as STO18-x) was investigated by Raman scattering as a function of x. The result indicates the ideal soft mode-type quantum ferroelectric phase transition of STO18-x, where the 18O exchange enhances the softening of the soft mode by the suppression of quantum fluctuation. In the vicinity of the quantum critical point (x approximately xc=33%), the system results in the ferroelectric-paraelectric phase coexistence state, in clear contrast to the homogeneous ferroelectric phase in STO18-x, whose x is sufficiently larger than xc. Simultaneously, the softening of the soft mode becomes strongly rounded with the underdamped oscillation. The present result indicates that the sensitivity of the soft phonon vibration to the mass disorder is dramatically enhanced in the vicinity of the quantum critical point.     

Extended study of molecular dynamics simulation of homogeneous vapor-liquid nucleation of water

Using the simple point charge/extended water model, we performed molecular dynamics simulations of homogeneous vapor-liquid nucleation at various values of temperature T and supersaturation S, from which the nucleation rate J, critical nucleus size n(*), and the cluster formation free energy DeltaG were derived. As well as providing lots of simulation data, the results were compared with theories on homogeneous nucleation, including the classical, semi-phenomenological, and scaled models, but none of these gave a satisfactory explanation for our results. It was found that two main factors made the theories fail: (1) The average cluster structure including the nonspherical shape and the core structure that is not like the bulk liquid and (2) the forward rate which is larger than assumed by the theories by about one order of magnitude. The quantitative evaluation of these factors is left for future investigations.     

Total synthesis of (+)-galanthamine starting from d-glucose

The stereoselective total synthesis of (+)-galanthamine (+)-1 starting from d-glucose is described. The cyclohexene ring in (+)-1 was prepared in an optically active form from d-glucose using Ferrier’s carbocyclization reaction, and the critical quaternary carbon was stereoselectively generated via chirality transfer based on the Claisen rearrangement of a cyclohexenol. The dibenzofuran skeleton was effectively constructed by the bromonium ion-mediated intramolecular cyclization of a cyclohexene possessing a phenolic ether function. After the introduction of a carbon-carbon double bond, the Pictet-Spengler type cyclization, followed by the reduction of the amide function completed the chiral synthesis of (+)-1.     

Novel bis(ethylenedithio)tetrathiafulvalene-based organic conductor with 1,1'-ferrocenedisulfonate

A new bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF)-based salt with a ferrocenyl moiety, alpha' '-(BEDT-TTF)(4)(Fe(C(5)H(4)SO(3))(2)).6H(2)O, has been prepared. The ferrocenyl part of this salt is neutral and diamagnetic, but the magnetic susceptibility is well modeled by a Curie-Weiss law with C = 0.142 emu.K.mol(-1) (approximately 1/3 of s = 1/2 spin). The spin is likely to be localized on the donor layer because of its unique charge disproportionation.     

Structural assignment of disialylated biantennary N-glycan isomers derivatized with 2-aminopyridine using negative-ion multistage tandem mass spectral matching

To investigate the possibility of structural assignment based on negative-ion multistage tandem mass (MS(n)) spectral matching, four isomers of disialylated biantennary N-glycans (alpha2-6 and/or alpha2-3 linked sialic acid on alpha1-6 and alpha1-3 antennae) derivatized with 2-aminopyridine (PA) were analyzed by employing high-performance liquid chromatography/electrospray ionization linear ion trap time-of-flight mass spectrometry (HPLC/ESI-LIT-TOFMS), which uses helium gas for ion trapping and collision-induced dissociation (CID). It is shown that the MS(2) spectra derived from each precursor ion [M-2H](2-) are reproducible and useful for distinguishing the four isomers. Thus, they can be assigned by negative-ion MS(2) spectral matching based on correlation coefficients. In addition, MS(3) spectra derived from D-type fragment ions clearly differentiate the alpha2-3- or alpha2-6-linked sialic acid on the alpha1-6 antenna due to their characteristic spectral patterns. The C(4)-type fragment ions, which are produced from both the alpha1-6 and alpha1-3 antennae, show the characteristic MS(3) spectra reflecting alpha2-3- or alpha2-6- linkage type or a mixture of both types. Thus, the differentiation and assignment of these disialylated biantennary N-glycan isomers can also be supported with the MS(3) spectra of C(4)- and D-type ions.