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11.
Sasamoto N Dubs C Hamashima Y Sodeoka M 《Journal of the American Chemical Society》2006,128(43):14010-14011
We have developed a highly efficient reaction for catalytic asymmetric addition of malonates to dihydroisoquinolines using chiral Pd(II) complexes. In the reactions, substrates with various substitution patterns were available, and the reactions were complete within several hours (<3 h in most cases) under mild reaction conditions, affording various optically active C1-substituted tetrahydroisoquinoline derivatives (up to 98% yield, up to 97% ee). Furthermore, slow addition of DDQ allowed the in situ generation of the reactive intermediate from the corresponding N-Boc-protected amine, and dehydrogenative addition reaction was successfully demonstrated. 相似文献
12.
Enantioselective Pd‐Catalyzed Allylic Alkylation Reactions of Dihydropyrido[1,2‐a]indolone Substrates: Efficient Syntheses of (−)‐Goniomitine, (+)‐Aspidospermidine,and (−)‐Quebrachamine 下载免费PDF全文
Beau P. Pritchett Jun Kikuchi Dr. Yoshitaka Numajiri Prof. Dr. Brian M. Stoltz 《Angewandte Chemie (International ed. in English)》2016,55(43):13529-13532
The successful application of dihydropyrido[1,2‐a]indolone (DHPI) substrates in Pd‐catalyzed asymmetric allylic alkylation chemistry facilitates rapid access to multiple alkaloid frameworks in an enantioselective fashion. Strategic bromination at the indole C3 position greatly improved the allylic alkylation chemistry and enabled a highly efficient Negishi cross‐coupling downstream. The first catalytic enantioselective total synthesis of (?)‐goniomitine, along with divergent formal syntheses of (+)‐aspidospermidine and (?)‐quebrachamine, are reported herein. 相似文献
13.
Oleg Tkachenko Abdur Rahim Andrey Baraban Ruslan Sukhov Inna Khristenko Yoshitaka Gushikem Yuriy Kholin 《Journal of Sol-Gel Science and Technology》2013,66(1):145-154
A sol–gel based hybrid process was developed by manipulating different techniques in sol–gel process to synthesize γ-alumina and (CuO, CuO + ZnO) doped γ-alumina spherical particles. Catalysts having spherical geometry have an important advantage over powders or pellets which are impervious to fluids, when packed in a reactor. Boehmite sol was used as alumina precursor for synthesizing porous γ-alumina and doped materials. γ-alumina particles having 5 wt% CuO, 4 wt% CuO + 1 wt% ZnO, 3 wt% CuO + 2 wt% ZnO and 2 wt% CuO + 3 wt% ZnO were prepared by adding required amounts of Cu(NO3)2 and Zn(NO3)2 solutions prior to gelation of the sol. Methanol dehydration studies were carried out by employing these synthesized catalysts. Hundred percent conversion of methanol to dimethyl ether was observed with (4 wt% CuO + 1 wt% ZnO)-γ-alumina and (5 wt% CuO)-γ-alumina microspheres at 325 and 350 °C, respectively. 相似文献
14.
Yoshitaka Ishimuro Fumiyuki Hamada Akio Nakajima 《Journal of polymer science. Part A, Polymer chemistry》1979,17(6):1811-1819
The scattering function of rods with a constant radius, 8 Å, and a length distribution of the Schulz–Zimm type was calculated on a computer as a model of helical synthetic polypeptide. The influence of length and length distribution on the scattered intensity of small-angle x-ray scattering was clarified. As length grows and length distribution broadens it is difficult to obtain reliable values of molecular weight and radius of gyration from a Zimm plot. The influence of length distribution on the mass per unit length, Mq, and the radius of gyration of the cross section, 〈S〉1/2, from the Guinier plot of the cross-sectional factor decreases as the length increases, and reliable values of Mq and 〈S〉1/2 can be obtained even for rods with wide distribution for rods more than 600 Å long. In particular, it is pointed out that the value of 〈S〉1/2 is little influenced by length and length distribution. 相似文献
15.
Yoshitaka Ogiwara Hitoshi Kubota Yuji Kimura 《Journal of polymer science. Part A, Polymer chemistry》1978,16(11):2865-2873
The influence of ferric acetylacetonate [Fe(acac)3] on the photodegradation of model compounds of polyethylene (PE) was examined. By studying electron-spin-resonance (ESR) spectra of photoirradiated compounds such as 1-octene and 1,7-octadiene, which contain carbon double bonds, Fe(acac)3 was found to accelerate the formation of allyl radical by contact with them. On the other hand, Fe(acac)3 suppressed the radical formation based on Norrish type I reaction in a carbonyl group of compounds such as 2-octanone and 3-octanone. Based on the study of ultraviolet (UV) spectra as well as ESR spectra on photoirradiated samples, the influence of Fe(acac)3 on the photodecomposition of model compounds of PE was discussed. Finally, the discussion turned to the mechanism of photodecomposition of PE in the presence of ferric salt. 相似文献
16.
The nature of the complex europium carbonate ion in concentrated carbonate solution was studied polarographically. A polarographic method for the determination of micro amounts of europium ion in the presence of diverse ions (and especially lanthanides) was developed. 相似文献
17.
The number of pigments in single light-harvesting complexes (chlorosomes) were calculated by imaging single chlorosomes in a frozen buffer at cryogenic temperature with a confocal laser fluorescence microscope and pigment extraction. Chlorosomes were isolated from two types of green photosynthetic bacteria Chlorobium (Chl.) tepidum and Chloroflexus (Cfl.) aurantiacus and were individually imaged in the frozen medium. Each fluorescence spot observed mainly came from a single chlorosome and was ascribable to self-aggregates of bacteriochlorophyll (BChl) c molecules as core parts of chlorosomes. A three-dimensional distribution of fluorescence of single chlorosomes was analyzed, and the number of chlorosomes in a volume of 54,000 microm(3) was counted directly. On the basis of the results, averaged numbers of the BChl c molecules contained in a single chlorosome of Chl. tepidum and Cfl. aurantiacus were determined to be 1.4 x 10(5) and 9.6 x 10(4), respectively. The present numbers are almost comparable to those estimated by other methods (Martinez-Planells et al., Photosynth. Res. 2002, 71, 83 and Monta?o et al., Biophys. J. 2003, 85, 2560). 相似文献
18.
19.
Terminal Hydride Species in [FeFe]‐Hydrogenases Are Vibrationally Coupled to the Active Site Environment 下载免费PDF全文
Dr. Cindy C. Pham Dr. David W. Mulder Dr. Vladimir Pelmenschikov Dr. Paul W. King Dr. Michael W. Ratzloff Dr. Hongxin Wang Nakul Mishra Dr. Esen E. Alp Dr. Jiyong Zhao Dr. Michael Y. Hu Dr. Kenji Tamasaku Dr. Yoshitaka Yoda Prof. Stephen P. Cramer 《Angewandte Chemie (International ed. in English)》2018,57(33):10605-10609
A combination of nuclear resonance vibrational spectroscopy (NRVS), FTIR spectroscopy, and DFT calculations was used to observe and characterize Fe?H/D bending modes in CrHydA1 [FeFe]‐hydrogenase Cys‐to‐Ser variant C169S. Mutagenesis of cysteine to serine at position 169 changes the functional group adjacent to the H‐cluster from a ‐SH to ‐OH, thus altering the proton transfer pathway. The catalytic activity of C169S is significantly reduced compared to that of native CrHydA1, presumably owing to less efficient proton transfer to the H‐cluster. This mutation enabled effective capture of a hydride/deuteride intermediate and facilitated direct detection of the Fe?H/D normal modes. We observed a significant shift to higher frequency in an Fe?H bending mode of the C169S variant, as compared to previous findings with reconstituted native and oxadithiolate (ODT)‐substituted CrHydA1. On the basis of DFT calculations, we propose that this shift is caused by the stronger interaction of the ‐OH group of C169S with the bridgehead ‐NH‐ moiety of the active site, as compared to that of the ‐SH group of C169 in the native enzyme. 相似文献
20.
Keiichiro Ishikawa Nobuyasu Hanari Yoshitaka Shimizu Toshihide Ihara Akira Nomura Masahiko Numata Takashi Yarita Kenji Kato Koichi Chiba 《Accreditation and quality assurance》2011,16(6):311-322
Purity assay of high-purity materials (HPMs) of phthalic acid esters (PAEs) was carried out by means of a mass balance method.
In this method, chromatographic methods such as gas chromatography-flame ionization detector (GC-FID) and/or high-performance
liquid chromatography (HPLC) in combination with other methods such as Karl-Fischer (KF) titration and vacuum evaporation
(VE) were applied. The sum of the impurities estimated by these methods allowed the estimation of the purity of the main component
by difference. Seven PAEs with varying side chain structures and levels of impurities were analysed on a systematic way in
which impurities were classified into several groups in terms of their abundance, availability of qualitative information
and availability of authentic compounds, etc. The absolute quantity of each impurity was determined by GC-FID and/or HPLC
based on the calibration made by the authentic compounds of impurities whenever available. The purities in mass fraction of
these PAEs were certified at the National Metrology Institute of Japan (NMIJ), and the PAEs were registered as primary reference
materials playing an essential role in linking the metrological traceability of the Japan Calibration Service System (JCSS)
to the International System of Units (SI). 相似文献