Chemoenzymatic synthesis of (+)-totarol, (+)-podototarin, (+)-sempervirol, and (+)-jolkinolides E and D

The enzymatic resolution products [(1R,4aR,8aR)-1,2,3,4,4a,5,6,7,8,8a-decahydro-5,5,8a-trimethyl-2-oxo-trans-naphthalene-1-methanol-2-ethylene acetal (8aR)-7 (98% ee) and {acetate of (1S,4aS,8aS)-1,2,3,4,4a,5,6,7,8,8a-decahydro-5,5,8a-trimethyl-2-oxo-trans-naphthalene-1-methanol-2-ethylene acetal} (8aS)-9 (>99% ee)] obtained by the lipase-catalyzed enantioselective acetylation of (±)-7 in the presence of vinyl acetate as an acyl donor were converted to the ,β-unsaturated ketones (8aR)-6 and (8aS)-6, respectively. Concise syntheses of (+)-totarol 1, (+)-podototarin 2 and (+)-sempervirol 3 were achieved based on Michael reactions between (8aS)-6 and the appropriate β-keto ester followed by aldol condensation. The first chiral syntheses of (+)-jolkinolides E 4 and D 5 were achieved from (5R,10R,12R)-12-hydroxypodocarpa-8(14)-en-13-one 15 derived from (8aR)-6.     

Effect of an electric field on defects in a nematic liquid crystal with variable surface anchoring

We report experimental studies on defects in a nematic liquid crystal with negative dielectric anisotropy mounted in a cell with perfluoropolymer-coated surfaces. The sample exhibits a discontinuous anchoring transition from planar to homeotropic on cooling at zero or a small electric field, and above a cross-over voltage a continuous ‘inverse Freedericksz transition’, at which the director starts tilting in opposite directions at the two surfaces. Defects of strength ±1/2 are either annihilated or expelled when the director tilts. On the other hand, disclination lines of ±1 which end in partial point defects (boojums) at the surfaces in the planar alignment regime acquire point defects of strength ±1 at the midplane of the cell when the director tilts. At a low enough temperature, the homeotropic anchoring becomes strong, and an electric field above the Freedericksz threshold generates the usual umbilic defects, which follow the dynamic scaling laws found in earlier studies.     

Heat of Terpolymerization

Abstract

A novel correlation for predicting the heat of terpolymerization from the binary data is proposed. This correlation is applicable to the ternary system with monomers which obey the Q-e scheme. The heat of terpolymerization for the ternary system methyl methacrylate-styrene-acrylonitrile is calculated from binary data.     

Internal radiocesium contamination of adults and children in Fukushima 7 to 20 months after the Fukushima NPP accident as measured by extensive whole-body-counter surveys

The Fukushima Dai-ichi NPP accident contaminated the soil of densely-populated regions in Fukushima Prefecture with radioactive cesium, which poses significant risks of internal and external exposure to the residents. If we apply the knowledge of post-Chernobyl accident studies, internal exposures in excess of a few mSv/y would be expected to be frequent in Fukushima.Extensive whole-body-counter surveys (n = 32,811) carried out at the Hirata Central Hospital between October, 2011 and November, 2012, however show that the internal exposure levels of residents are much lower than estimated. In particular, the first sampling-bias-free assessment of the internal exposure of children in the town of Miharu, Fukushima, shows that the ¹³⁷Cs body burdens of all children (n = 1,383, ages 6–15, covering 95% of children enrolled in town-operated schools) were below the detection limit of 300 Bq/body in the fall of 2012. These results are not conclusive for the prefecture as a whole, but are consistent with results obtained from other municipalities in the prefecture, and with prefectural data.     

Facile synthesis of graft copolymers containing rigid poly(dialkyl fumarate) branches by macromonomer method

Graft copolymers show microphase separated structure as seen in block copolymers and have lower intrinsic viscosity than block copolymers because of a branching structure. Therefore, considering molding processability, especially for polymers containing rigid segments, graft copolymers are useful architectures. In this work, graft copolymers containing rigid poly(diisopropyl fumarate) (PDiPF) branches were synthesized by full free‐radical polymerization process. First, synthesis of PDiPF macromonomers by addition‐fragmentation chain transfer (AFCT) was investigated. 2,2‐Dimethyl‐4‐methylene‐pentanedioic acid dimethyl ester was found to be an efficient AFCT agent for diisopropyl fumarate (DiPF) polymerization because of the suppression of undesired primary radical termination, which significantly took place when common AFCT agent, methyl 2‐(bromomethyl)acrylate, was used. Copolymerization of PDiPF macromonomer with ethyl acrylate accomplished the generation of the graft copolymer having flexible poly(ethyl acrylate) backbone and rigid PDiPF branches. The graft copolymer showed a microphase separated structure, high transparency, and characteristic thermal properties to PDiPF and poly(ethyl acrylate). © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2474–2480     

MAO‐free and extremely active catalytic system for ethylene tetramerization

The original Sasol catalytic system for ethylene tetramerization is composed of a Cr source, a PNP ligand, and MAO (methylaluminoxane). The use of expensive MAO in excess has been a critical concern in commercial operation. Many efforts have been made to replace MAO with non‐coordinating anions (e.g., [B(C₆F₅)₄]^?); however, most of such attempts were unsuccessful. Herein, an extremely active catalytic system that avoids the use of MAO is presented. The successive addition of two equivalent [H(OEt₂)₂]⁺[B(C₆F₅)₄]^? and one equivalent CrCl₃(THF)₃ to (acac)AlEt₂ and subsequent treatment with a PNP ligand [CH₃(CH₂)₁₆]₂C(H)N(PPh₂)₂ ( 1 ) yielded a complex presumably formulated as [ 1 ‐CrAl (acac)Cl₃(THF)]²⁺[B(C₆F₅)₄]^?₂, which exhibited high activity when combined with iBu₃Al (1120 kg/g‐Cr/h; ~4 times that of the original Sasol system composed of Cr (acac)₃, iPrN(PPh₂)₂, and MAO). Via the introduction of bulky trialkylsilyl substituents such as –SiMe₃, –Si(nBu)₃, or –SiMe₂(CH₂)₇CH₃ at the para‐position of phenyl groups in 1 (i.e., by using [CH₃(CH₂)₁₆]₂C(H)N[P(C₆H₄‐p‐SiR₃)₂]₂ instead of 1 ), the activities were dramatically improved, i.e., tripled (2960–3340 kg/g‐Cr/h; more than 10 times that of the original Sasol system). The generation of significantly less PE (<0.2 wt%) even at a high temperature is another advantage achieved by the introduction of bulky trialkylsilyl substituents. NMR studies and DFT calculations suggest that increase of the steric bulkiness on the alkyl‐N and P‐aryl moieties restrict the free rotation around (alkyl)N–P (aryl) bonds, which may cause the generation of more robust active species in higher proportion, leading to extremely high activity along with the generation of a smaller amount of PE.