Treatment of the thioethers (RNH-o-C 6 H 4 ) 2 S (H 2 [R 2 NSN]; R ) Xy, Xyf; Xy ) 3,5-Me 2 C 6 H 3 , Xyf ) 3,5-(CF 3 ) 2 C 6 H 3 ) with 2 equiv of n-BuLi followed by addition of 0.5 equiv of [(η 6 -C 6 H 6 )-RuCl 2 ] 2 in THF gave the bis(diarylamido)/thioether complexes [(η 6 -C 6 H 6 )Ru[R 2 NSN]] (R ) Xy (1a), R ) Xyf (1b)) in moderate yields. In the presence of 1a (1 mol %) and PCy 3 (2 mol %; Cy ) cyclohexyl), benzonitrile was catalytically hydrogenated to give benzylamine (72%) and benzylidenebenzylamine (27%) at 80 °C and 30 atm, while the hydrogenation with 1b as a catalyst precursor resulted in the formation of benzylamine (37%) and benzylidenebenzylamine (51%) under the same reaction conditions. The yield of benzylamine was improved up to 92% by using a catalyst mixture of 1a (1 mol %)/PCy 3 (2 mol %)/t-BuONa (10 mol %). On the other hand, the reaction of 1a with excess PMe 3 afforded the tris(trimethylphosphine) derivative [(PMe 3 ) 3 Ru[Xy 2 NSN]] (2). Treatment of 2 with excess PhCN, MeCN, or N 2 H 4 ‚ H 2 O resulted in the replacement of a PMe 3 ligand by these substrates to give [(PMe 3 ) 2 LRu-[Xy 2 NSN]] (3, L ) PhCN; 4, L ) MeCN; 5, L ) N 2 H 4 ), while the reaction of 2 with benzoylhydrazine gave the κ 2 -benzoylhydrazido complex [(PMe 3 ) 2 Ru(κ 2 -(O,N)-PhC(O)d NNH 2 )(H[Xy 2 NSN])] (6). Structures of 1a, 1b, 2, 5, and 6 have been determined by X-ray crystallography.

Discovery and development of enzymes for the synthesis of chiral amines have been a hot topic for basic and applied aspects of biocatalysts. Based on our X‐ray crystallographic analyses of porcine kidney D‐amino acid oxidase (pkDAO) and its variants, we rationally designed a new variant that catalyzed the oxidation of (S)‐4‐Cl‐benzhydrylamine (CBHA) from pkDAO and obtained it by functional high‐throughput screening with colorimetric assay. The variant I230A/R283G was constructed from the variant R283G which had completely lost the activity for D‐amino acids, further gaining new activity toward (S)‐chiral amines with the bulky substituents. The variant enzyme (I230A/R283G) was characterized to have a catalytic efficiency of 1.85 s−1 for (S)‐CBHA, while that for (R)‐1‐phenylethylamine was diminished 10‐fold as compared with the Y228L/R283G variant. The variant was efficiently used for the synthesis of (R)‐CBHA in 96 % ee from racemic CBHA by the deracemization reaction in the presence of reducing agent such as NaBH4 in water. Furthermore, X‐ray crystallographic analysis of the new variant complexed with (S)‐CBHA, together with modelling study clearly showed the basis of understanding the structure‐activity relationship of pkDAO.

Liquid-crystalline compounds having carbon -carbon double bonds were synthesized and subjected to hydrosilylation using poly(hydrosi1oxane)s as silylating agents and hexachloroplatinic acid as a catalyst. Even though the silylating agents were polymeric and the mesogenic compounds carried bulky groups as their side chains, the presence of a spacer (polymethylene chain) diminished the steric hindrance and the reaction was possible. Among the mesogens 1-(4 '-ally1oxybenzoyloxy)-4-(4 "-methoxybenzoy1oxy)phenylene is a new compound, and its synthesis is described in detail. The final products were side-chain-type liquidcrystalline polymers, that is, mesogenic group-grafted poly(siloxane)s, and a few of their liquid-crystalline properties are also elucidated.

The copolymerization of vinyl acetate (VAc) with 1,2‐polybutadiene (1,2‐PB; 85.5% 1,2‐units and 14.5% 1,4‐units) as a multivinyl monomer was carried out at 80 °C in dioxane with dimethyl 2,2′‐azobisisobutyrate (MAIB) at high concentrations (0.10–0.50 mol/L) as an initiator. The copolymerization of 1,2‐PB [0.80 mol/L (monomer unit)] and VAc (1.20 mol/L) with MAIB (0.30 mol/L) for 4 h proceeded homogeneously without gelation to yield a soluble copolymer. The resulting copolymer was divided into methanol‐ and n‐hexane‐insoluble parts, of which the yields based on the total weight of the comonomers and initiator were 46 and 20%, respectively. The methanol‐insoluble part consisted of the fractions of the 1,2‐PB units with (9 mol %) and without (39 mol %) an intact double bond, the 1,4‐PB unit (8 mol %), the VAc unit (32 mol %), and the methoxycarbonylpropyl group (12 mol %) as the MAIB fragment, whereas the hexane‐insoluble one was composed of the fraction of the 1,2‐PB units with (4 mol %) and without (17 mol %) a double bond, the 1,4‐PB unit (4 mol %), the VAc unit (60 mol %), and the methoxycarbonylpropyl group (15 mol %). The use of higher concentrations of 1,2‐PB and VAc and lower concentrations of MAIB resulted in gelation. The cast film from a chloroform solution of the methanol‐insoluble part contained spherical pores organized in a hexagonal way with a monodisperse pore size of 3 μm. The copolymer molecules seemed to be arranged in an ordered way on the surface layer of the pores, as shown by an optical microscopy image under crossed polarizers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2328–2337, 2006

Three ester-type low molecular-weight liquid crystals having vinyl groups were synthesized and subjected to hydrosilylation, i.e., the reaction with polysiloxanes carrying hydrosilyl groups using a platinum compound as a catalyst. The thermotropic nature of the resultant liquid crystalline polymers (LCPs) was characterized. The application of the electric field changed the optical transparency of the LCPs. The effects of the applied voltage, the sample thickness and the frequency were studied. The results were explained by the theory developed for low molecular-weight liquid crystals, but a few different behaviors were also recognized. The observed electro-optic effects strongly suggest that the LCPs are not suitable as materials for displays due to slower responses, which are inherent in polymeric liquids.