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91.
Copper-catalyzed oxonium ylide formation-[2,3] shift of (5S,7R)-5-allyloxy-1-diazo-8-(p-methoxybenzyloxy)-7-methyl-2-octanone (3) proceeded in tetrahydrofuran-dichloromethane (4 : 1) under reflux with an excellent stereoselectivity (97 : 3) to give (2R,6S)-2-allyl-6-[(2R)-3-(p-methoxybenzyloxy)-2-methylpropyl]-3-dihydropyranone (2) as a major isomer in 82% yield. The resultant pyranone (2) was converted to the key intermediate (1) of the Mulzer's laulimalide synthesis and its derivatives (14, 15). 相似文献
92.
Iwaoka M Komatsu H Katsuda T Tomoda S 《Journal of the American Chemical Society》2004,126(16):5309-5317
To investigate the nature of nonbonded Se...O interactions, three series of 2-substituted benzeneselenenyl derivatives [2-(CHO)C6H4SeX (1), 2-(CH2OH)C6H4SeX, (2), 2-(CH2OiPr)C6H4SeX (3); X = Cl, Br, CN, SPh, SeAr, Me] were synthesized. The 17O NMR absorption observed for 17O-enriched aldehydes 1 appeared upfield relative to benzaldehyde (PhCHO), while the opposite downfield shifts relative to benzyl alcohol (PhCH2OH) were observed for 17O-enriched alcohols 2 and ethers 3. The magnitude of both the upfield and the downfield shifts became larger as the electron-withdrawing ability of a substituent X increased. Quantum chemical calculations at the B3LYP level revealed that for all model compounds the most stable conformer has an intramolecular nonbonded Se.O interaction. Thus, the relative 17O NMR chemical shifts (DeltadeltaO) for 1-3 would reflect the strengths of the Se...O interactions. The natural bond orbital (NBO) analysis demonstrated that the stabilization energy due to an nO --> sigma Se-X orbital interaction (ESe...O) correlates with the Se...O atomic distance on a single curve irrespective of the type of the O atom. On the other hand, the atoms in molecules (AIM) analysis showed that the nonbonded Se...O interactions can be characterized by the presence of a bond critical point, the total energy density (HSe...O) of which decreases with strengthening of the interaction. The results suggested that Se...O interactions have a dominant covalent character rather than an electrostatic one. 相似文献
93.
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
94.
Van Truong Do Hiroyuki Hirakata Takayuki Kitamura Van Thanh Vuong Van Lich Le 《International Journal of Solids and Structures》2012,49(13):1676-1684
A novel method combining the experimental data at only two different mixed mode fractures and an empirical interface toughness function has been proposed to establish the interfacial toughness function of a bimaterial in submicron scale. The modified four-point bend specimen was used in experiment to evaluate the first type of mixed mode fracture, while the sandwiched cantilever specimen was employed to get the second one. An empirical interface toughness function reflecting quite accurately the delamination behavior was adopted as a typical one. The obtained results investigated that the proposed method could be used to calibrate not only the interfacial fracture criteria at pure modes but also at any mixed mode fracture of bimaterials in submicron scale. 相似文献
95.
We proposed a novel kinetic energy decomposition analysis based on information theory. Since the Hirshfeld partitioning for electron densities can be formulated in terms of Kullback–Leibler information deficiency in information theory, a similar partitioning for kinetic energy densities was newly proposed. The numerical assessments confirm that the current kinetic energy decomposition scheme provides reasonable chemical pictures for ionic and covalent molecules, and can also estimate atomic energies using a correction with viral ratios. 相似文献
96.
Prof. Dr. Tomoaki Tanase Dr. Kanako Nakamae Haruka Miyano Prof. Dr. Yasuyuki Ura Prof. Dr. Yasutaka Kitagawa Dr. Shiho Yada Prof. Dr. Tomokazu Yoshimura Prof. Dr. Takayuki Nakajima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(47):12078-12103
A series of the octapalladium chains supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) ligands, [Pd8(meso-dpmppm)4(L)2](BF4)4 (L=none ( 1 ), solvents: CH3CN ( 2 a ), dmf ( 2 b ), dmso ( 2 c ), RN≡C: R=Xyl ( 3 a ), Mes ( 3 b ), Dip ( 3 c ), tBu ( 3 d ), Cy ( 3 e ), CH3(CH2)7 ( 3 f ), CH3(CH2)11 ( 3 g ), CH3(CH2)17 ( 3 h )) and [Pd8(meso-dpmppm)4(X)2](BF4)2 (X=Cl ( 4 a ), N3 ( 4 b ), CN ( 4 c ), SCN ( 4 d )), were synthesized by using 2 a as a stable good precursor, and characterized by spectroscopic (IR, 1H and 31P NMR, UV-vis-NIR, ESI-MS) measurements and X-ray crystallographic analyses (for 1 , 2 a , b , 3 a , b , e , f , 4 a – d ). On the basis of DFT calculations on the X-ray determined structure of 2 b ( [2b-Pd8]4+ ) and the optimized models [Pd8(meso-Ph2PCH2P(H)CH2P(H)CH2PH2)4(CH3CN)2]4+ ( [Pd8Ph8]4+ ) and [Pd8(meso-H2PCH2P(H)CH2P(H)CH2PH2)4(CH3CN)2]4+ ( [Pd8H8]4+ ), with and without empirically calculating dispersion force stabilization energy (B3LYP-D3, B3LYP), the formation energy between the two Pd4 fragments is assumed to involve mainly noncovalent interactions (ca. −70 kcal/mol) with four sets of interligand C−H/π interactions and Pd⋅⋅⋅Pd metallophilic one, while electron shared covalent interactions are almost canceled out within the Pd8 chain. All the compounds isolated are stable in solution and exhibit characteristic absorption at ∼900 nm, which is assignable to a spin allowed HOMO to LUMO transition, and shows temperature dependent intensity change with variable absorption coefficients presumably due to coupling with some thermal vibrations. The structures and electronic states of the Pd8 chains are found finely tunable by varying the terminal capping ligands. In particular, theoretical calculations elucidated that the HOMO-LUMO energy gap is systematically related to the central Pd−Pd distance (2.7319(6)–2.7575(6) Å) by two ways with neutral ligands L ( 1 , 2 , 3 ) and with anionic ligands X ( 4 ), which are reflected on the NIR absorption energy of 867–954 nm. The isocyanide terminated Pd8 complexes ( 3 ) further reacted with excess of RNC (6 eq) to afford the Pd4 complexes, [Pd4(meso-dpmppm)2(RNC)2](BF4)2 ( 13 ), and the cyclic voltammograms of 2 a (L=CH3CN), 3 , and 13 (R=Xyl, Mes, tBu, Cy) demonstrated wide range redox behaviors from 2{Pd4}4+ to 2{Pd4}0 through 2{Pd4}2+↔{Pd8}4+, {Pd8}3+, and {Pd8}2+ strings. The oxidized complexes, [Pd4(meso-dpmppm)2(RNC)3](BF4)4 ( 16 ), were characterized by X-ray analyses, and the two-electron reduced chain of [Pd8(meso-dpmppm)4](BF4)2 ( 7 ) was analyzed by spectroscopic and electrochemical techniques and DFT calculations. Reactions of 2 a with 1 equiv. of aromatic linear bisisocyanide (BI) in CH2Cl2 deposited insoluble coordination polymers, {[Pd8(meso-dpmppm)4(BI)](BF4)4}n ( 5 ), and interestingly, they were soluble in acetonitrile, 31P{1H} and 1H DOSY NMR spectra as well as SAXS curves suggesting that the coordination polymers may exist in acetonitrile as dynamically 1D self-assembled coordination polymers comprising ca. 50 units of the Pd8 rod averaged within the timescale. 相似文献
97.
98.
Yusuke Yoshimura Ryuichiro Hibi Akiho Nakata Moeka Togashi Shoujiro Ogawa Takayuki Ishige Mamoru Satoh Fumio Nomura Tatsuya Higashi 《Biomedical chromatography : BMC》2019,33(7)
A liquid chromatography/electrospray ionization–tandem mass spectrometry‐based method was developed for the identification of the conjugation positions of the monoglucuronides of 25‐hydroxyvitamin D3 [25(OH)D3] and 24,25‐dihydroxyvitamin D3 [24,25(OH)2D3] in human urine. The method employed derivatization with 4‐(4‐dimethylaminophenyl)‐1,2,4‐triazoline‐3,5‐dione to convert the glucuronides into fragmentable derivatives, which provided useful product ions for identifying the conjugation positions during the MS/MS. The derivatization also enhanced the assay sensitivity and specificity for urine sample analysis. The positional isomeric monoglucuronides, 25(OH)D3‐3‐ and ‐25‐glucuronides, or 24,25(OH)2D3‐3‐, ‐24‐ and ‐25‐glucuronides, were completely separated from each other under the optimized LC conditions. Using this method, the conjugation positions were successfully determined to be the C3 and C24 positions for the glucuronidated 25(OH)D3 and 24,25(OH)2D3, respectively. The 3‐glucuronide was not present for 24,25(OH)2D3, unlike 25(OH)D3, thus we found that selective glucuronidation occurs at the C24‐hydroxy group for 24,25(OH)2D3. 相似文献
99.
100.
Absorption and photoluminescence (PL) spectra, PL quantum efficiency, and PL lifetime have been investigated on bis(8-hydroxyquinoline)
zinc (Znq2) and magnesium (Mgq2) in solutions and powder. Znq2 and Mgq2 have the lowest-energy absorption band at 376 and 396 nm in acetonitrile solution, respectively, and emission band with peak
at 555 and 480 nm. The PL quantum efficiency is 0.03 and 0.45 for Znq2 and Mgq2 in the solution, respectively, while 0.45 and 0.36 in powder. Unlike the case of powders, two PL lifetimes are obtained in
solutions. The longer lifetime is attributed to molecule having interaction with its neighboring molecule, while the shorter
one to the isolated single molecule. 相似文献