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341.
Single‐Step Construction of the anti‐Deoxypropionate Motif from Propylene: Formal Total Synthesis of the Cuticular Hydrocarbons Isolated from Antitrogus parvulus
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Toshiki Murayama Prof. Kyoko Nozaki 《Angewandte Chemie (International ed. in English)》2018,57(35):11394-11398
Reported herein is the single‐step construction of an anti‐configured deoxypropionate motif by syndiospecific propylene oligomerization catalyzed by a Cs‐symmetric zirconocene complex. After oligomerization, oxidation of the oligomers by oxygen afforded oligopropylene alcohols in a single step. This strategy was applied to the single‐step preparation of rel‐(2R,4S,6R,8S)‐2,4,6,8‐tetramethylundecan‐1‐ol, the racemic mixture of the synthetic fragment of the cuticular hydrocarbons isolated from the cane beetle Antitrogus parvulus. 相似文献
342.
Circularly Polarized Luminescence of Chiral Pt(pppb)Cl (pppbH=1‐pyridyl‐3‐(4,5‐pinenopyridyl)benzene) Aggregate in the Excited State
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Saori Tanaka Dr. Kyohei Sato Kyoko Ichida Dr. Taichi Abe Prof. Taro Tsubomura Prof. Takayoshi Suzuki Prof. Kazuteru Shinozaki 《化学:亚洲杂志》2016,11(2):265-273
We prepared enantiomers of chiral PtII complexes, Pt(pppb)Cl and Pt(pppb)CN (pppbH=1‐pyridyl‐3‐(4,5‐pinenopyridyl)benzene), and measured their CPL (circularly polarized luminescence) spectra for excimer and trimer emission. The contribution of the pinene moiety to CPL was considerably low for the π–π* emission of the monomer but large for MMLCT (metal‐metal‐to‐ligand charge‐transfer) of the excimer and trimer which had a helical structure induced in a face‐to‐face stacking fashion. The trimer CPL for (+)‐Pt(pppb)Cl was larger in intensity than that of excimer CPL; on the other hand, that for (+)‐Pt(pppb)CN was opposite in sign compared with that of excimer CPL. We conclude that differences in the excited‐state structure of the aggregate between Pt(pppb)Cl and Pt(pppb)CN account for the variation in the CPL spectra. By the aid of TD‐DFT calculations it was predicted that the dihedral angle θ(Cl‐Pt‐Pt‐Cl) was 50–60° or 110–140° for Pt(pppb)Cl aggregates and 160° for Pt(pppb)CN aggregates. 相似文献
343.
Takuto Ohsato Dr. Yuri Okuno Prof. Dr. Shintaro Ishida Prof. Dr. Takeaki Iwamoto Dr. Ka‐Ho Lee Prof. Dr. Zhenyang Lin Prof. Dr. Makoto Yamashita Prof. Dr. Kyoko Nozaki 《Angewandte Chemie (International ed. in English)》2016,55(38):11426-11430
A potassium diboryllithate (B2LiK) was synthesized and structurally characterized. DFT calculations, including NPA and AIM analyses of B2LiK, revealed ionic interactions between the two bridging boryl anions and Li+ and K+. Upon standing in benzene, B2LiK deprotonated the solvent to form a hydroborane and a phenylborane. On the basis of DFT calculations, a detailed reaction mechanism, involving deprotonation and hydride/phenyl exchange processes, is proposed. An NBO analysis of the transition state for the deprotonation of benzene suggests that the deprotonation should be induced by the coordination of benzene to the K+. 相似文献
344.
Maeda Y Ito T Suzuki A Kurono Y Ueta A Yokoi K Sumi S Togari H Sugiyama N 《Rapid communications in mass spectrometry : RCM》2007,21(5):799-806
Tandem mass spectrometry (MS/MS) has become a prominent method for screening newborns for diseases such as organic acidemia and fatty acid oxidation defects, although current methods cannot separate acylcarnitine isomers. Accurate determination of dicarboxylic acylcarnitines such as methylmalonylcarnitine and glutarylcarnitine has not been carried out, because obtaining standards of these acylcarnitines is difficult. We attempted the individual determinations of acylcarnitines with isomers and dicarboxylic acylcarnitines by applying high-performance liquid chromatography (HPLC). Chromatographic separation was performed by gradient elution using a mixture of 0.08% aqueous ion-pairing agent and acetonitrile as the mobile phase. Mass transitions of m/z 161.8-->84.8 for carnitine and m/z 164.8-->84.8 for deuterated carnitine were monitored in positive ion electrospray ionization mode. One carnitine and 16 acylcarnitines were quantified. The limit of quantitation (LOQ) was 0.1 micromol/L for methylmalonylcarnitine and 0.05 micromol/L for the other acylcarnitines. Intra-day and inter-day coefficients of variance (CVs) were <8.3% and <8.8%, respectively, for all acylcarnitines in serum, and both were <9.2% in urine. Mean recoveries were >90% for all acylcarnitines. Human samples were quantified by this method. After addition of deuterated acylcarnitines as internal standards, acylcarnitines in serum or urine were extracted using a solid-phase extraction cartridge. In healthy adult individuals, isobutyryl-, 2-methylbutyryl- and isovalerylcarnitine were detected in serum and urine. Dicarboxylic acylcarnitines were detected in urine. High concentrations of methylmalonylcarnitine and propionylcarnitine were found in both the serum and the urine of a patient with methylmalonic acidemia. The described HPLC/MS/MS method could separate most acylcarnitine isomers and quantify them, potentially allowing detailed diagnoses and follow-up treatment for those diseases. 相似文献
345.
A kinetic study has been made of the BF(3)-mediated ring opening of two rigid conformers (alpha and beta) of m- and p-dimethyl-substituted homobenzoquinone epoxides spiro-linked with a twist-boat dibenzocycloheptene ring as compared with the conformationally mobile epoxides bearing diphenyl groups. The rates of the regioselective ring opening were dependent on the topological alignment of the dibenzocycloheptene ring as well as the substitution pattern of the quinone dimethyl groups, indicating pi-aryl participated orbital interaction with the vacant Walsh orbital of the oxirane ring. 相似文献
346.
Chiral macrocycles with the hydrogen bond donor/acceptor sites in the cavity were synthesized and covalently bonded to silica gel to give chiral stationary phases (CSPs), which showed excellent abilities to resolve various chiral compounds, such as benzoin and Co(acac)3, in HPLC. Various organic solvents could be used as the mobile phase to optimize the resolution efficiency of CSPs, and in some cases, even MeCN, MeOH, and CO(2) could be used for the complete resolution of enantiomers. 相似文献
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350.
The standard enthalpy of formation of novel chemical species — crystalline cationic surfactant molecular complexes — was studied to elucidate the bonding nature, serially scanning over the different surfactant chain-length homologs and various additive species. The enthalpy was not large, but was obviously dependent on the surfactant chain length and the chemical nature of the additive species. The typical complexes comprising long alkyl chain surfactants were formed endothermally, while in short alkyl chain homologs the process was exothermic. By examining the thermal aspect, it was suggested that the typical complexes of long alkyl-chain surfactants were derived not from attractive energetic force factors, but rather from entropic factors associated with the occurrence of severe disorder caused by heavy thermal agitation in the complex crystalline state. 相似文献