Synthetic studies of an 18-membered antitumor macrolide, tedanolide. 5. Stereoselective synthesis of the C13-C23 part via condensation of two fragments, C13-C17 and C18-C21, by taking advantage of the 3,4-dimethoxybenzyl protecting group.

An efficient and stereoselective synthesis of the C13-C23 part (8) was achieved starting from methyl (R)- and (S)-3-hydroxy-2-methylpropionates (9) via coupling of the C13-C17 aldehyde (6), prepared by Evans asymmetric aldol reaction, with the C18-C21 iodoalkene (5b) by taking advantage of the 3,4-dimethoxybenzyl protecting group.     

Theoretical Study on the Second Hyperpolarizabilities for Small Radical Systems

We study the second hyperpolarizabilities (ɣ) for anion, neutral and cation radicals and find that magnitudes of ɣ (| ɣ |) of the radicals are sensitively influenced by features of each charged state. It is also found that electron-correlation dependence of ɣ could be related to the resonance structure contributing to the ground state of the molecules.This paper was originally presented at the 5th International Conference on NEAR FIELD OPTICS and RELATED TECHNOLOGIES (NFO-5), which was held on December 6–10, 1998 at Coganoi Bay Hotel, Shirahama, Japan, in cooperation with the Japan Society of Applied Physics and Mombusho Grant-in Aid for Scientific Research on Priority Areas “Near-field Nano-optics” Project, sponsored by Japan Society for the Promotion of Science.     

Optimized structures of Cr2(CO)6+ with three different symmetries by density functional calculation

Density functional calculations have been made on a binuclear metal carbonyl ion Cr₂(CO)₆⁺ found in our laser ablation–molecular beam (LAMB) experiment. Optimized structures are calculated for three different conformations: T33 of D_3d symmetry with three terminal carbonyl groups on each chromium atom, B2T22 of D_2h symmetry with two bridging carbonyl groups and two terminal carbonyl groups on each chromium atom, and B4T11 of D_4h symmetry with four bridging carbonyl groups and one terminal carbonyl group on each chromium atom. The most stable conformation is T33 which is 36.76 and 286.44 kJ mol⁻¹ lower in energy than B2T22 and B4T11, respectively. The difference of conformation exerts a significant influence on the internuclear distance between chromium and the carbon of terminal CO, but hardly on the Cr–Cr bond length. For B2T22 and B4T11, longer C–O distances for bridging carbonyls compared with those for terminal ones indicate effective π*-back donation from the chromium atom to the bridging carbonyl groups. Furthermore, the relative abundance of Cr₂(CO)_n⁺ (n = 0–6) observed in our previous experimental study can be explained qualitatively by comparison of the excess energy produced in the formation of a Cr⁺–Cr bond with the CO dissociation energy of Cr₂(CO)₆⁺. © 1998 John Wiley & Sons, Ltd.     

Stabilization of p-Phenylenebis(N-tert-butylaminoxyl) Relative to p-Benzoquinonediimine N,N′-Dioxide

Steric interactions between methoxy and tert -butyl groups are the reason that 2 only exists as p-phenylenebis(N-tert-butylaminoxyl) B . The p-phenylenebis(N-tert-butylaminoxyl) 1 has the p-quinonediimine N,N′-dioxide structure Q in solution as well as in the crystalline state.     

Three-dimensional arbitrary Lagrangian–Eulerian numerical prediction method for non-linear free surface oscillation

A numerical prediction method has been proposed to predict non-linear free surface oscillation in an arbitrarily-shaped three-dimensional container. The liquid motions are described with Navier–Stokes equations rather than Laplace equations which are derived by assuming the velocity potential. The profile of a liquid surface is precisely represented with the three-dimensional curvilinear co-ordinates which are regenerated in each computational step on the basis of the arbitrary Lagrangian–Eulerian (ALE) formulation. In the transformed space, the governing equations are discretized on a Lagrangian scheme with sufficient numerical accuracy and the boundary conditions near the liquid surface are implemented in a complete manner. In order to confirm the applicability of the present computational technique, numerical simulations are conducted for the free oscillations of viscid and inviscid liquids and for highly non-linear oscillation. In addition, non-linear sloshing motions caused by horizontal and vertical excitations and a transition from non-linear sloshing to swirling are numerically predicted in three-dimensional cylindrical containers. Conclusively, it is shown that these sloshing motions associated with high non-linearity are reasonably predicted with the present numerical technique. © 1998 John Wiley & Sons, Ltd.     

Conformation and dynamics of fibrous and membrane proteins as revealed by high-resolution solid-state nuclear magnetic resonance

We examined conformation and dynamics of a variety of fibrous and membrane proteins by means of the conformation-dependent displacements of ¹³C nuclear magnetic resonance (NMR) chemical shifts and their relaxation parameters, respectively, as recorded by high-resolution solid-state ¹³C NMR. Determination of three-dimensional structure of atomic resolution is also briefly described for a simple peptide on the basis of precise measurements of interatomic distances.