Catalytic asymmetric total synthesis of (+)-lactacystin

Total synthesis of (+)-lactacystin, a potent and selective proteasome inhibitor, was accomplished using a catalytic enantioselective Strecker reaction of a ketoimine as the initial key step. An enone-derived N-phosphinoyl ketoimine 7 was selected as a stable masked alpha-hydroxy ketoimine analogue. Excellent enantioselectivity (98% ee) and practical catalyst activity were produced under the optimized catalyst preparation method using 2.5 mol % Gd{N(SiMe3)2}3 as a metal source and 3.8 mol % D-glucose-derived ligand 8. This reaction was conducted on a 5 g scale. The chiral tetrasubstituted C-5 carbon efficiently controlled the stereochemistry of the other three chiral centers of lactacystin. Chelation-controlled Meerwein-type reduction of ketone 5 using i-PrMgBr (originally reported by Kang in a related substrate) selectively produced the desired secondary alcohol at the C-9 position. The C-6 hydroxy and C-7 methyl groups were introduced via a silyl conjugate addition followed by the Tamao oxidation and Donohoe methylation, respectively, in a highly stereoselective manner. A practical amount of enantiomerically pure clasto-lactacystin beta-lactone (2), the biologically active form of (+)-lactacystin, can be synthesized using this route. clasto-Lactacystin beta-lactone (2) was converted to (+)-lactacystin following the reported procedure.     

Synthesis and Applications of (ONO Pincer)Ruthenium‐Complex‐Bound Norvalines

Two (ONO pincer)ruthenium‐complex‐bound norvalines, Boc?[Ru(pydc)(terpy)]Nva?OMe ( 1 ; Boc=tert‐butyloxycarbonyl, terpy=terpyridyl, Nva=norvaline) and Boc?[Ru(pydc)(tBu‐terpy)]Nva?OMe ( 5 ), were successfully synthesized and their molecular structures and absolute configurations were unequivocally determined by single‐crystal X‐ray diffraction. The robustness of the pincer Ru complexes and norvaline scaffolds against acidic/basic, oxidizing, and high‐temperature conditions enabled us to perform selective transformations of the N‐Boc and C?OMe termini into various functional groups, such as alkyl amide, alkyl urea, and polyether groups, without the loss of the Ru center or enantiomeric purity. The resulting dialkylated Ru‐bound norvaline, n‐C₁₁H₂₃CO?l ‐[Ru(pydc)(terpy)]Nva?NH‐n‐C₁₁H₂₃ (l ‐ 4 ) was found to have excellent self‐assembly properties in organic solvents, thereby affording the corresponding supramolecular gels. Ru‐bound norvaline l ‐ 1 exhibited a higher catalytic activity for the oxidation of alcohols by H₂O₂ than parent complex [Ru(pydc)(terpy)] ( 11 a ).     

Anomalous thermochromic transition of poly(di‐n‐octylsilane)

The thermochromic behavior of poly(di‐n‐octylsilane) {[Si(C₈H₁₇)₂]_n; PDOS} was studied by ultraviolet (UV) absorption, differential scanning calorimetry, and X‐ray diffraction measurements. The structure of PDOS in the low‐temperature phase strongly depended on not only the temperature but also the rate of cooling, that is, the thermal history. Temperature‐dependent UV absorption spectra were highly dependent on thermal hysteresis. Cooled rapidly (10 K/min), PDOS showed two absorption peaks at 3.32 and 3.51 eV in low‐temperature‐ordered phases, whereas a single absorption peak at 3.32 eV became predominant with slow cooling (0.3 K/min). The appearance of the two peaks at low temperatures suggested that a mixture of different conformations was introduced by rapid cooling. A fiber diffraction pattern measured at 240 K after rapid cooling also showed evidence of the existence of novel conformation. A temperature‐dependent powder X‐ray diffraction pattern changed significantly between 270 and 280 K. Rapid cooling reduced the intensity of the X‐ray diffraction peak in this temperature region. This intensity change was explained by the conformational mixture in the polymer. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1085–1092, 2001     

Layer structure estimation of three‐dimensional crystal and two‐dimensional molecular film for fluorinated comb copolymers

Comb copolymers containing both hydrogenated and fluorinated side‐chains were prepared by copolymerization using acrylic or methacrylic monomers in several ratios. The crystal structures of these copolymers and layer structures of their organized molecular films were investigated by wide‐angle X‐ray diffraction (WAXD), small‐angle X‐ray scattering (SAXS), and out‐of plane X‐ray diffraction. Further, to selectively estimate the regularity of shorter fluorocarbon side‐chains, organized molecular films of copolymers were investigated by polarized near‐edge X‐ray adsorption fine structure (NEXAFS) spectroscopy. From the results of these measurements, it was inferred that these copolymers formed highly ordered layer structures, and a long spacing was predominantly determined by the arrangement of hydrogenated side‐chains, except in copolymers having extremely high fluorocarbon contents. In the case of the organized molecular films, the fluorinated side‐chains of methacrylate copolymers cannot form a highly ordered arrangement, whereas those of acrylate copolymers were oriented on monolayers. However, in both cases, the hydrogenated side‐chains predominantly formed layer structures in the organized films, and the fluorinated side‐chains did not contribute to the formation of the layer structures. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 534–546, 2008     

Synthesis of boradiazaindacene-imidazopyrazinone conjugate as lipophilic and yellow-chemiluminescent chemosensor for superoxide radical anion

As a chemiluminescent chemosensor that emits yellow light on reacting with a superoxide radical anion (O₂⁻) and has a lipophilic character, a 6-phenylimidazo[1,2-a]pyrazin-3(7H)-one derivative possessing a boradiazaindacene (BODIPY) at the para position of 6-phenyl (1) was synthesized. The lipophilicity of 1 was investigated by reversed-phase liquid chromatography, and its log P_ow value was found to be 3.57. This value was much higher than that of 2-methyl-6-(4-methoxypheyl)imidazo[1,2-a]pyrazin-3(7H)-one (MCLA, log P_ow=1.19) and 6-[4-[2-{N′-(5-fluoresceinyl)thioureido}ethoxy]phenyl]-2-methylimidazo[1,2-a]pyrazin-3(7H)-one (FCLA, log P_ow=−0.08), and it was comparable to that of benzenoid hydrocarbons. The O₂⁻-induced chemiluminescence of 1 was investigated using the hypoxanthine/xanthine oxidase system as the source of O₂⁻, and as a result, yellow emission was observed. The maximum wavelength was observed at 542 nm, and it was longer than that of FCLA.     

Distributivity and stationary reflections

In this paper, we present some relations between generalized distributivity of quotient algebras and Mahlo operations, and show that the distributivity implies some variants of stationary relections.

     

Biaxial nematic phase of crank-like bis(β-diketonato)copper(II) complexes established by X-ray diffraction and Z-value calculations

We have synthesized a series of six novel bis(β-diketonate)copper (II) complexes, 1a, 1b, 2a, 2b, 3a, and 3b, substituted by two bulky substituents in the short molecular axis direction to investigate their mesomorphism. The m,p,m'-trimethoxylphenyl-substituted derivatives, 2a and 2b, and the m,p-dimethoxylphenyl-substituted derivatives, 3a and 3b, did not show mesomorphism, whereas each of the p-methoxyphenyl-substituted derivatives 1a and 1b only showed a nematic phase, which was revealed from polarizing microscopic observations. We established from X-ray diffraction and Z-value calculations that each of the crank-like derivatives 1a and 1b forms a rectangular parallelepiped dimer and shows a biaxial nematic phase.