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91.
[structure: see text] A second generation total synthesis of the potent antitumor agent (+)-phorboxazole A (1) has been achieved. The cornerstone of this approach comprises a more convergent strategy, involving late-stage Stille union of a fully elaborated C(1-28) macrocycle with a C(29-46) side chain. The second generation synthesis entails the longest linear sequence of 24 steps, with an overall yield of 4.2%. 相似文献
92.
[reaction: see text] This paper describes a novel method to synthesize a quinoline backbone by incorporating allenyl cations into a catalytic intramolecular Friedel-Crafts reaction. The initial products were isomerized and aromatized upon treatment with acid and base, respectively, to give quinolines. The basic concept also proved to be promising for 1-benzazepine, 1-benzazocine, or isoquinoline synthesis. 相似文献
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96.
Sekino E Kumamoto T Tanaka T Ikeda T Ishikawa T 《The Journal of organic chemistry》2004,69(8):2760-2767
(-)-Quinine-catalyzed intramolecular oxo-Michael addition (IMA) of 7-hydroxy-5-methoxy-8-tigloylcoumarins was developed for the enantioselective construction of 2,3-dimethyl-4-chromanone systems in the context of the asymmetric synthesis of anti-HIV-1 active Calophyllum coumarins. Combination of the IMA and MgI(2)-assisted demethylation of the 5-methoxy group along with isomerization of the formed chromanone systems as key steps successfully led to the concise synthesis of (+)-inophyllum B and (+)-calanolide A, possible candidates for AIDS drugs. Further examination of the asymmetric IMA with cinchona alkaloids lacking a methoxy group on the quinoline skeleton suggested the influence of the methoxy substituent on stereoselectivity at the stereogenic centers of the chromanone systems. 相似文献
97.
Wagner J. Barreto Henrique de Santana Flaveli A. S. Almeida Dilson N. Ishikawa Yoshio Kawano 《Journal of Analytical and Applied Pyrolysis》2003,70(2):719-210
The synthesis, characterization, and thermal decomposition of the [Ni(SCN)2(H+SCN)2(4-mepy)2] compound with an octahedral structure in polymeric chain were reported, in which SCN groups form bridges among Ni(II) ions. The compound decomposes in water resulting in a pH<4 solution. The FT-IR spectrum presented doublet bands at 2117; 2128 cm−1, 788; 773 cm−1 assigned to ν(C---N) and ν(C---S) stretching modes, respectively, and δ(SCN) deformation modes at 468; 476 cm−1. The Raman spectrum of the compound presented the ν(C---N) stretching as a strong doublet at 2122; 2128 cm−1, ν(C---S) at 783; 770 cm−1, and δ(SCN) at 468; 477 cm−1. No significant changes were observed in the 4-mepy ligand bands compared with the vibrational frequencies of the pure compound or the compound in aqueous solution 0.2 mol l−1. The crystal UV–vis reflectance spectrum presented two bands centered in 626 and 424 nm tentatively assigned to the d→d type transitions, 3A2g→3T1g and 3A2g→3T1g, for a symmetry close to Oh. The TG curve showed a mass loss between 120 and 200 °C assigned to the loss of the two 4-mepy molecules; from 200 to 265 °C, the loss of the two H+SCN groups; and from 265 to 450 °C, the loss of the two SCN groups that formed the bridges among the nickel atoms. Based on these mass loss data, a mechanism of thermal decomposition for the compound was proposed. 相似文献
98.
Fukuji Higashi Shigeru Sugimori Toshio Mashimo 《Journal of polymer science. Part A, Polymer chemistry》1988,26(4):1003-1009
The direct polyesterification with thionyl chloride (SOCl2) in pyridine was further investigated. Copolycondensations of dicarboxylic acids, bisphenols, and hydroxybenzoic acids were significantly affected by the reaction temperatures and combinations of monomers which could change relative rates of alcoholyses of the activated dicarboxylic acids and the hydroxyacids consequently to vary monomer sequences in the copolymers resulted. The sequences were tried to be varied more directly by stepwise reactions of monomers in copolycondensations of dicarboxylic acids, bisphenols, and p-hydroxybenzoic acid (PHB), as well as PHB and m-hydroxybenzoic acid (MHB). The reactions proceeded smoothly and satisfactorily when carried out by initial reaction of dicarboxylic acids and PHB followed by bisphenols likely to favor sequential to random distributions of monomers. Reverse addition of PHB and bisphenols, and then dicarboxylic acids resulted in rapid precipitation due to some oligomerization of PHB at an earlier stage of reaction, and largely retarded the reaction. This was also the case for the copolycondensation of PHB and MHB. Copolymers of high inherent viscosities with up to 65 mol% PHB could be obtained by initial reaction of MHB followed by PHB. 相似文献
99.
Fukuji Higashi Toshio Mashimo 《Journal of polymer science. Part A, Polymer chemistry》1986,24(7):1697-1701
The reaction promoted by thionyl chloride and pyridine could selectively activate carboxyl groups of hydroxybenzoic acids to give polyesters of high inherent viscosities up to 3.8. Favorable conditions were studied in terms of the temperatures for the initial reaction with the acids and subsequent aging at room temperature. Copolymers of several combinations of hydroxybenzoic acids with high molecular weights were obtained in quantitative yield by carrying out the polycondensation at 80°C for 3 h. The reaction could also produce high molecular polyesters in a simpler process without the initial activation of dicarboxylic acids by adding a mixture of these monomers to the condensing agent, and a tough film- and fiberforming polymer was obtained from 4,4′-dihydroxyphenylsulfone of low nucleophilicity whose polymer of high molecular weight is difficult to obtain. The process was also successfully applied to the direct copolycondensations of hydroxybenzoic acids, aromatic dicarboxylic acids, and bisphenols to produce polyesters of ηinh up to 5.6. 相似文献
100.
Fukuji Higashi Michihide Ozawa Akihiko Mochizuki 《Journal of polymer science. Part A, Polymer chemistry》1986,24(4):637-643
The reaction promoted by diphenyl chlorophosphate (DPCP) in pyridine was successfully applied to the preparation of soluble aromatic copolyesteramides of high molecular weights directly from aromatic dicarboxylic acids, bisphenols, and a wide range of mol % aromatic diamines. Dropwise addition of a mixture of bisphenols and diamines (more favorably of bisphenols and then diamines) to the mixture of dicarboxylic acids activated by DPCP led the reactions homogeneously even with high mol % of diamines to produce copolymers of good solubility. This improved copolymer solubility was roughly estimated by sequence distribution of polyamide and polyester units in the copolymers, which was studied in a model reaction and in the copolycondensations by simultaneous and stepwise addition of bisphenols and diamines. 相似文献