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51.
Hamada T Chieffi A Ahman J Buchwald SL 《Journal of the American Chemical Society》2002,124(7):1261-1268
A new catalyst system for the enantioselective alpha-arylation of ketones is reported. This catalyst, prepared from Pd(2)(dba)(3) and a bulky dialkylphosphino-binaphthyl ligand, is able to effect the asymmetric arylation of ketone enolates with aryl bromides utilizing NaO(t)()Bu as base. These new catalysts enjoy much higher reactivity than previous systems; arylation reactions could be effected at room temperature with only 2 mol % of the Pd catalyst. The coupling of alpha-alkyl-alpha'-protected cyclopentanones proceeded in high yield, and the resulting quaternary stereogenic center was installed in up to 94% ee. 相似文献
52.
53.
Isao Takahashi Fumika Morita Shunsuke Kusagaya Haruhiko Fukaya Osamu Kitagawa 《Tetrahedron: Asymmetry》2012,23(24):1657-1662
In the presence of an (R)-MOP-Pd2(dba)3 catalyst, the reaction of ortho-tert-butylaniline with 2-bromophenyl arylethynyl ketone proceeded via a tandem amination (1,4-addition of aniline to an ynone and subsequent intramolecular Buchwald–Hartwig amination) to afford axially chiral N-(2-tert-butylphenyl)-2-aryl-4-quinolinone derivatives with moderate enantioselectivity (up to 72% ee). 相似文献
54.
Assembly of submicron-sized microspheres has received much attention due to its high potential for wide variety of applications. We have developed a preparation method of polymer particles by simple mixing of a poor solvent into the polymer solution followed by evaporation of a good solvent. By using this technique, silica nanoparticles and polymer composite particles were prepared. Preparation of three-dimensional assemblies of silica particles in polymer particles and composite Janus particles are shown. 相似文献
55.
General acid‐catalyzed reaction can be enhanced by the addition of base. Self‐catalyzed esterification of benzoic acid and octan‐1‐ol was enhanced by the addition of certain base such as imidazole. The rate of the esterification was accelerated as the concentration of imidazole increased. Trans‐esterification of 4‐nitrophenyl acetate was promoted in chloroform by the mixture of benzoic acid and imidazole, but not by benzoic acid or imidazole alone. 相似文献
56.
Prof. Tomoaki Tanase Miho Tanaka Mami Hamada Yuka Morita Dr. Kanako Nakamae Prof. Yasuyuki Ura Prof. Takayuki Nakajima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8219-8224
A new linear tetraphosphine containing a PNP phosphazane bridge, rac-bis[(diphenylphosphinomethyl)phenylphosphino]phenylamine (rac-dpmppan), was synthesized and utilized to support a series of Pd/Pt mixed metal tetranuclear chains, [Pd4−nPtn(μ-rac-dpmppan)2(XylNC)2](PF6)2 (XylNC=xylyl isocyanide; n=0: Pd4 ( 1 ), 1: PtPd3 ( 2 ), 2: PtPd2Pt ( 3 ), 2: Pt2Pd2 ( 4 ), 3: Pt2PdPt ( 5 )), in which the number and positions of additional Pt atoms were successfully controlled depending on the respective synthetic procedures using transformations from 1 to 3 through 2 and from 4 to 5 by redox-coupled exchange reactions. The 31P{1H} NMR and ESI mass spectra and X-ray diffraction analyses revealed almost identical tetranuclear structures, with slight contraction of metal-metal bonds according to incorporation of Pt atoms. The electronic absorption spectra of 1 – 5 exhibited characteristic bands at 635–510 nm with an energy propensity depending on the number and positions of Pt centres, which were assigned to HOMO (dσ*σσ*) to LUMO (dσ*σ*σ*) transition by theoretical calculations. The present results demonstrated that the electronic structures of Pd/Pt mixed-metal tetranuclear complexes are finely tuned as orbital-overlapping alloyed metal chains by atomically precise Pt incorporation in the Pd4 chain. 相似文献
57.
58.
Measurements from instruments are sometimes censored at or below the instrument’s lower or upper limit of detection because the instruments have a calibrated response only over a certain data range. Near the ends of the range, the system reports a censored value such as “measurand value is less than threshold,” or “measurand value is more than threshold.” How should one analyze data that includes such “less than” and/or “more than” results and what is the impact of such censoring on estimation of variance components? To answer these two questions, this article makes three contributions: (1) It illustrates a straightforward numerical Bayesian analysis of such censored data based on the likelihood function, (2) it provides a simulation study to show the impact of increased amounts of censoring, and (3) it shows that if the true likelihood has an unknown form for measurand values near the threshold and another known form away from the threshold, then it is prudent for the measurement system to report censored values rather than actual values. Open source software to analyze censored data is provided as supplementary material. 相似文献
59.
Shunsuke Shimo Dr. Kohei Takahashi Prof. Nobuharu Iwasawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(15):3790-3794
A new chiral probe molecule for mono-alcohols is developed by using 1,2-dihydro-1-hydroxy-2,3,1-benzodiazaborine (DAB) bearing an acridine moiety 1 . In the presence of mono-alcohols, DAB 1 forms borate 2 by boronic ester formation, followed by coordination of the acridine moiety to the boron atom. Borate 2 has a chiral center on the boron atom and works as a stereodynamic circular dichroism (CD) probe molecule for chiral mono-alcohols based on the π–π interaction between the acridine moiety and the carbon–carbon unsaturated moiety on mono-alcohols. 相似文献
60.
Taishi Nakanishi Dr. Jun Kikuchi Dr. Atsushi Kaga Prof. Dr. Shunsuke Chiba Prof. Dr. Masahiro Terada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(37):8230-8234
A catalytic enantioselective synthesis of β-amino secondary amides was achieved using vinyl azides as the enamine-type nucleophile and chiral N-Tf phosphoramide as the chiral Brønsted acid catalyst through a five-step sequential transformation in one pot. The established sequential transformation involves an enantioselective [4+2] cycloaddition reaction of vinyl azides with N-acyl imines as the key stereo-determining step that is efficiently accelerated by a chiral N-Tf phosphoramide catalyst in a highly enantioselective manner in most cases. Further generation of the iminodiazonium ion intermediate through ring opening of the cycloaddition product and subsequent skeletal rearrangement involving Schmidt-type 1,2-aryl group migration followed by recyclization of the resulting nitrilium ion were also initiated by the same acid catalyst. Final acid hydrolysis of the recyclized products in the same pot gave rise to enantioenriched β-amino amides through C−C bond formation at the α-position of the secondary amides. 相似文献