Stereoselective and Enantioselective Syntheses of the Four Stereoisomers of Muscol from (3RS)‐Muscone

Two trans stereoisomers of 3‐methylcyclopentadecanol (=muscol), (1R,3R)‐ 2 and (1S,3S)‐ 2 , were efficiently synthesized from (3RS)‐3‐methylcyclopentadecanone (=muscone; (3RS)‐ 1 ) by a highly stereoselective reduction (Scheme). L‐Selectride^® (=lithium tri(sec‐butyl)borohydride) was used, followed by the enantiomer resolution by lipase QLG (Alcaligenes sp.). The cis stereoisomers of muscol, (1S,3R)‐ 2 and (1R,3S)‐ 2 , were obtained by the Mitsunobu inversion of (1R,3R)‐ 2 and (1S,3S)‐ 2 , respectively (Scheme). The absolute configuration of (1R,3R)‐ 2 was determined by X‐ray crystal‐structure analysis of its 3‐nitrophthalic acid monoester, 2‐[(1R,3R)‐3‐methylcyclopentadecyl hydrogen benzene‐1,2‐dicarboxylate ((1R,3R)‐ 3b ), and by oxidation of (1R,3R)‐ 2 to (3R)‐muscone.     

Fraunhofer Diffraction Pattern by a Slit Aperture between a Knife Edge and a Metal Cylinder

The Fraunhofer diffraction pattern of an aperture formed between a knife edge and a smooth surface of a turned metal cylinder or half cylinder is different from the diffraction pattern of an ideal slit aperture. The diffraction pattern is simulated by adding the light reflected by the cylinder surface to the pattern formed by a slit, and is measured using a cylinder that has been partly cut away so that it can represent either a full or half cylinder. The theoretical and measured patterns agree well with each other.     

Catalytic enantioselective synthesis of atropisomeric 2-aryl-4-quinolinone derivatives with an N–C chiral axis

In the presence of an (R)-MOP-Pd₂(dba)₃ catalyst, the reaction of ortho-tert-butylaniline with 2-bromophenyl arylethynyl ketone proceeded via a tandem amination (1,4-addition of aniline to an ynone and subsequent intramolecular Buchwald–Hartwig amination) to afford axially chiral N-(2-tert-butylphenyl)-2-aryl-4-quinolinone derivatives with moderate enantioselectivity (up to 72% ee).     

Efficient transformation of 7,14-dihydroxy-ent-kaurenes to novel ent-abietanes having cis-fused α-methylene γ-lactones under Mitsunobu reaction conditions and their cytotoxicities

Transformation of plant-origin 7,14-dihydroxy-ent-kaurenes to ent-abietanes having a cis-fused α-methylene γ-lactones was accomplished efficiently under the Mitsunobu reaction conditions. The yields of the desired products were apparently influenced by the steric hindrance at C-1. The cytotoxic activity on P388 murine leukemia cells of the ent-abietanes having cis-fused α-methylene γ-lactones produced were assayed.     

The first halogen-substituted cyclotrigermenes: a unique halogen walk over the three-membered ring skeleton and facial stereoselectivity in the Diels-Alder reaction

Dark red crystals of the halogen-substituted cyclotrigermenes [(tBu3Si)3Ge3X; X = Cl, Br, I] were obtained in good yields by the reaction of [(tBu3Si)3Ge3]+.TTFPB- (TTFPB- = tetrakis(2,3,5,6-tetrafluorophenyl)borate) with potassium halides (KCl, KBr, or KI) in diethyl ether. The crystal structures of the halogen-substituted cyclotrigermenes reveal a cis-bent Ge=Ge double bond, caused by the introduction of the electronegative halogen atom on the sp3 germanium atom of cyclotrigermene. In solution, an intramolecular halogen migration over the three-membered ring skeleton was observed. Facial stereoselectivity in the Diels-Alder reaction of new cyclotrigermenes with 2,3-dimethyl-1,3-butadiene is also reported.     

Synthesis of novel liquid crystals having the perfluoropyrrolidino group

Novel liquid crystals which have the perfluoropyrrolidino group, a heterocyclic perfluoroalkyl group, and which show smectic phases have been synthesized with perfluoro-(2-pyrrolidinopropionyl fluoride) as one of the starting materials. Analogues with a polymerizable functional group also have been prepared and polymerized to give side chain liquid crystal polymers.     

Muon spin relaxation studies of magnetic-field-induced effects in high-Tc superconductors

Muon spin relaxation measurements in high transverse magnetic fields [FORMULA: SEE TEXT] revealed strong field-induced quasistatic magnetism in the underdoped and Eu-doped (La,Sr)2CuO4 and La1.875Ba0.125CuO4, existing well above Tc and TN. The susceptibility counterpart of Cu spin polarization, derived from the muon spin relaxation rate, exhibits a divergent behavior towards T approximately 25 K. No field-induced magnetism was detected in overdoped La1.81Sr0.19CuO4, optimally doped Bi2212, and Zn-doped YBa2Cu3O7.     

Structural analysis of Si(1 1 1)-√21 × √21-(Ag, Au) surface by using reflection high-energy positron diffraction

The Au adsorption induced √21 × √21 super-lattice structure on the Si(1 1 1)-√3 × √3-Ag structure has been investigated using reflection high-energy positron diffraction. The height of the Au adatom was determined to be 0.59 Å from the underlying Ag layer from the rocking curve analysis with the dynamical diffraction theory. The adatoms were preferentially situated at the center of the large Ag triangle of the inequivalent triangle structure of the Si(1 1 1)-√3 × √3-Ag substrate. From the intensity distribution in the fractional-order Laue zone, the in-plane coordinate of the Au adatoms was obtained.     

Surface structure of In/Si(1 1 1) studied by reflection high-energy positron diffraction

We have investigated a quasi-one-dimensional structure of In/Si(1 1 1) surface using reflection high-energy positron diffraction (RHEPD), which is sensitive to the topmost surface structure under the total reflection condition. From the rocking curves, we found that In atoms are located at two different vertical positions, i.e., 0.99 Å and 0.55 Å from the Si zigzag chain in both 4 × 1 (210 K) and 8 × 2 (60 K) phases.     

Atomic structure of two-dimensional binary surface alloys: Si(111)-√21 × √21 superstructure

The atomic structures of Au and Ag co-adsorption-induced √21 × √21 superstructure on a Si(111) surface, i.e., (Si(111)-√21 × √21-(Au, Ag)), where the Si(111)-5 × 2-Au surface is used as a substrate, have been investigated using reflection high-energy positron diffraction (RHEPD) and photoemission spectroscopy. From core-level spectra, we determined the chemical environments of Ag and Au atoms present in the Si(111)-√21 × √21-(Au, Ag) surface. From the rocking curve and pattern analyses of RHEPD, we found that the atomic coordinates of the Au and Ag atoms were approximately the same as those of the Au and Ag atoms in other Si(111)-√21 × √21 surfaces with different stoichiometries. On the basis of the core-level and RHEPD results, we revealed the atomic structure of the Si(111)-√21 × √21-(Au, Ag) surface.