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[reaction: see text] A short, high-yielding synthesis of the C-glucoside 8,10-di-O-methylbergenin is reported. Key elements of the synthesis are a stereoselective installation of a beta-C-aryl linkage, a palladium(0)-catalyzed aryl carbonylation, and a regioselective lactonization reaction. This pathway should allow access to a host of bergenin analogues. 相似文献
64.
Kubo K Akemoto M Anderson S Aoki T Araki S Bane KL Blum P Corlett J Dobashi K Emma P Frisch J Fukuda M Guo Z Hasegawa K Hayano H Higo T Higurashi A Honda Y Iimura T Imai T Jobe K Kamada S Karataev P Kashiwagi S Kim E Kobuki T Kotseroglou T Kurihara Y Kuriki M Kuroda R Kuroda S Lee T Luo X McCormick DJ McKee B Mimashi T Minty M Muto T Naito T Naumenko G Nelson J Nguyen MN Oide K Okugi T Omori T Oshima T Pei G Potylitsyn A Qin Q Raubenheimer T Ross M Sakai H Sakai I Schmidt F Slaton T Smith H 《Physical review letters》2002,88(19):194801
Electron beams with the lowest, normalized transverse emittance recorded so far were produced and confirmed in single-bunch-mode operation of the Accelerator Test Facility at KEK. We established a tuning method of the damping ring which achieves a small vertical dispersion and small x-y orbit coupling. The vertical emittance was less than 1% of the horizontal emittance. At the zero-intensity limit, the vertical normalized emittance was less than 2.8 x 10(-8) rad m at beam energy 1.3 GeV. At high intensity, strong effects of intrabeam scattering were observed, which had been expected in view of the extremely high particle density due to the small transverse emittance. 相似文献
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The regioselectivity of the nitrous acid mediated dealkylation of 4-substituted-N-ethyl-N-methylanilines is a function of the acidity of the reaction mixture. At high acidity deethylation predominates, whereas demethylation is the predominant reaction in nitrosamine formation at pH 2 and above. In some cases the regioselectivity of nitrosative dealkylation changes as the run proceeds. Through the use of the corresponding 4-nitroaniline as the primary substrate, CIDNP, kinetics, kinetic deuterium isotope effects and other transformations involving nitrosations with NO2 or NOBF4 in aprotic solvents, a new mechanism of tertiary amine nitrosation has been deduced and proposed to explain regioselective deethylation. The mechanism involves the oxidation of the substrate to the amine radical cation by NO+. This is followed by the abstraction of a hydrogen atom from the carbon adjacent to the amine nitrogen by NO2 to produce an iminium ion which reacts further to produce the corresponding aldehyde and the nitrosamine. Depending upon the acidity, this process competes with three other mechanistic pathways, two of which give the nitrosamine through the iminium ion, and one leads to the formation of C-nitro compounds. The competing pathways to nitrosamine formation involve NOH elimination from a nitrosammonium ion and deprotonation of the radical cation to give an alpha-amino radical which rapidly oxidized to the iminium ion. Predominant, but not highly regioselective demethylation occurs by these pathways. Nitro compound formation principally arises from the reaction of NO2 with the radical cation followed by deprotonation, but also occurs by para C-nitrosation followed by oxidation. 相似文献
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Brown EJ Whitwood AC Walton PH Duhme-Klair AK 《Dalton transactions (Cambridge, England : 2003)》2004,(16):2458-2462
The butoxy- and methoxy-derivatives (HLc, and HLb, respectively) of 1-[(ethoxycarbonyl)methyl]-3-hydroxy-2-(1H)-pyridinone, HLa, were synthesized by transesterification and the mononuclear complexes [MoO2(L(a-c))2] were obtained by the reaction of the ligands with molybdenyl acetylacetonate. The three complexes were fully characterized by (1)H and (13)C NMR spectroscopy, mass spectrometry and elemental analyses. A variable temperature NMR study showed that the N-substituents do not have a significant influence on the racemisation process of the complexes. The comparison of the crystal structure of [MoO2(Lb)2] with [MoO2(La)2] confirmed that an additional methylene group does not affect the immediate coordination environment of the molybdenum centre. The methoxy-derivative HLb was also found to produce a dinuclear complex of composition [(MoO2(Lb)O)2], the structure of which was determined by X-ray diffraction. 相似文献
69.
The crystal structure of 2,6-di(Pr(i))aniline hydrochloride contains hydrogen-bonded cubanes analogous to those in the complexes [M(2+)(2,6-di(Pr(i))C6H5N(2-))]4, M = Sn, Pb. 相似文献