A highly stereoselective synthesis of 11Z-retinal using tricarbonyliron complex

A stereoselective synthesis of 11Z-retinal 2, which is the chromophore of visual pigment (rhodopsin), was accomplished from the beta-ionylideneacetaldehyde-tricarbonyliron complex 3. The Peterson reaction of 3 using ethyl trimethylsilylacetate smoothly proceeded to afford predominantly the Z-ester 6. Transformation of the Z-ester 6 to the methyl ketone 19, followed by the Emmons-Horner reaction of 19 with C2-cyanophosphonate, produced ethyl 11Z, 13E-retinonitrile-tricarbonyliron complex 21 as the only product. Decomplexation of 21 with CuCl2 and subsequent DIBAL reduction gave 11Z-retinal 2 in excellent yield. Mechanistic consideration of Z-selectivity in the Peterson reaction of the aldehyde-tricarbonyliron complex is also discussed.     

Classification of extremal contractions from smooth fourfolds of -type

We investigate divisorial contractions of extremal rays from
smooth fourfolds. When the exceptional divisor is contracted to a curve, we prove that the divisor is a -bundle or quadric bundle over a smooth curve and the contraction is the blowing up along the curve. Furthermore we determine the local analytic structure of the contraction.

     

The phase boundary between α′- and tetragonal Ce

The phase boundary between the α'- and tetragonal high-pressure polymorphs of cerium was determined from the resistance anomaly. The phase boundary has a negative slope, ∂T/∂P = -7.56°C/kbar and appears to intersect the fusion curve in the neighborhood of the broad minimum.     

Laser magnetic resonance for the v = 1 ← 0 transition of SeO (X3Σ−) by a CO2 laser

The vibration-rotation transitions for a fundamental band of SeO (X³Σ^?) were studied by means of the infrared laser magnetic resonance (LMR) method employing a CO₂ laser. The LMR spectra arising from five SeO isotopic species except ⁷⁴SeO were detected and analyzed. Band origins for these species were determined. Molecular parameters ω_e, ω_eχ_e, B_e, and α_e, were obtained with the aid of the reduced mass relations. For ⁷⁷SeO the axial component of magnetic hyperfine interaction was obtained.     

Estimation of 4s covalent bonding of Fe2+ and Fe3+ ions in NiO

The charge densities of the 4s electrons in Fe²⁺ and Fe³⁺ ions in the ionic compound, NiO, were measured from an internal conversion experiment and compared with some predicted values on the basis of different theoretical methods.     

Evidence for a kaon-bound state K(-)pp produced in K(-) absorption reactions at rest

We have searched for a deeply bound kaonic state by using the FINUDA spectrometer installed at the e(+)e(-) collider DAPhiNE. Almost monochromatic K(-)'s produced through the decay of phi(1020) mesons are used to observe K(-) absorption reactions stopped on very thin nuclear targets. Taking this unique advantage, we have succeeded to detect a kaon-bound state K(-)pp through its two-body decay into a Lambda hyperon and a proton. The binding energy and the decay width are determined from the invariant-mass distribution as 115(+6)(-5)(stat)(+3)(-4)(syst) MeV and 67(+14)(-11)(stat)(+2)(-3)(syst) MeV, respectively.     

Determination of optical isomers for left-handed or right-handed chiral double-wall carbon nanotubes

The handedness relationship between adjacent layers in nested double-wall carbon nanotubes (DWNTs) has been investigated for the first time. Our high-resolution electron microscopy analysis on a series of specimen tilts can successfully tell the handedness of each constituent nanotube in a DWNT, and therefore the chiral indices (n, m) including their optical isomers [(n, m) or (m, n)] of inner and outer nanotubes can be uniquely determined. It is shown that right-handed and left-handed nanotubes are equally distributed for both the inner and outer nanotubes in the examined specimens and a preferable handedness relationship between the adjacent layers in DWNT may exist.     

Novel stereoselective entry to 2'-beta-carbon-substituted 2'-deoxy-4'-thionucleosides from 4-thiofuranoid glycals

2'-Beta-methyl- and 2'-beta-hydroxymethyl-2'-deoxy-4'-thionucleosides have been synthesized through PhSeCl-mediated electrophilic glycosidation using 4-thiofuranoid glycals having carbon substituents at the C2-position as a glycosyl donor. Preparation of these glycals were carried out by means of the C2 lithiation of 1-chloro-4-thiofuranoid glycal with LTMP followed by the Birch reduction of the chlorine atom. [reaction: see text]