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951.
Complementary α-alkylation approaches for a sterically hindered spiro[pyrazolopyranpiperidine]ketone
Chris Limberakis Jianke Li Gayatri Balan David A. Griffith Daniel W. Kung Colin Rose Derek Vrieze 《Tetrahedron letters》2012,53(20):2543-2547
Complementary α-alkylation methods are used to derivatize a sterically hindered spiro[pyrazolopyranpiperidine]ketone. More specifically, enolate alkylations in the presence of DMPU and aldol condensations are employed to deliver these compounds. 相似文献
952.
Bo Qu Nizar Haddad Sonia Rodriguez Heewon Lee Shengli Ma Xingzhong Zeng Diana C. Reeves Kanwar P.S. Sidhu Jon C. Lorenz Nelu Grinberg Carl A. Busacca Dhileepkumar Krishnamurthy Chris H. Senanayake 《Tetrahedron letters》2012,53(15):1982-1986
A novel trans-diastereoselective reductive amination of 4-substituted cyclohexanones is described using 9-BBN as reducing agent in the presence of FeCl3. The method permits efficient synthesis of structurally diverse 4-trans-alkoxycyclohexylamines. 相似文献
953.
Chris Walpole Ziping Liu Ernest E. Lee Hua Yang Fei Zhou Nicole Mackintosh Magnus Sjogren David Taylor Jinyu Shen Robert A. Batey 《Tetrahedron letters》2012,53(24):2942-2947
A diastereoselective synthesis of fluoropiperidine quinazoline spirocycles has been developed through a silyl triflate mediated intermolecular coupling of difluorobenzamidine and racemic N-protected 3-fluoropiperidine dimethyl ketals or piperidones. Combination of the silyl reagents together with Lewis acids (such as BF3·OEt2, ZnCl2, InCl3, etc.) accelerated the coupling reaction to afford the desired fluorospirocycles in good yields (40–83%) and high diastereoselectivity. A ratio of the two diastereoisomers of up to 10:1 in favor of the desired isomer can be achieved. 相似文献
954.
The reaction of terbium and europium salts with the lacunary polyxometalate (POM) [As(2)W(19)O(67)(H(2)O)](14-) and 2-picolinic acid (picH) affords the ternary lanthanoid-organic-polyoxometalate (Ln-org-POM) complexes [Tb(2)(pic)(H(2)O)(2)(B-β-AsW(8)O(30))(2)(WO(2)(pic))(3)](10-) (1), [Tb(8)(pic)(6)(H(2)O)(22)(B-β-AsW(8)O(30))(4)(WO(2)(pic))(6)](12-) (2), and [Eu(8)(pic)(6)(H(2)O)(22)(B-β-AsW(8)O(30))(4)(WO(2)(pic))(6)](12-) (3). A detailed synthetic investigation has established the conditions required to isolate pure bulk samples of the three complexes as the mixed salts H(0.5)K(8.5)Na[1]·30H(2)O, K(4)Li(4)H(4)[2]·58H(2)O, and Eu(1.66)K(7)[3]·54H(2)O, each of which has been characterized by single crystal X-ray diffraction. Complexes 2 and 3 are isostructural and can be considered to be composed of two molecules of 1 linked through an inversion center with four additional picolinate-chelated lanthanoid centers. When irradiated with a laboratory UV lamp at room temperature, compounds K(4)Li(4)H(4)[2]·58H(2)O and Eu(1.66)K(7)[3]·54H(2)O visibly luminesce green and red, respectively, while compound H(0.5)K(8.5)Na[1]·30H(2)O is not luminescent. A variable temperature photophysical investigation of the three compounds has revealed that both the organic picolinate ligands and the inorganic POM ligands sensitize the lanthanoid(III) luminescence, following excitation with UV light. However, considerably different temperature dependencies are observed for Tb(III) versus Eu(III) through the two distinct sensitization pathways. 相似文献
955.
Meyer FM Collins JC Borin B Bradow J Liras S Limberakis C Mathiowetz AM Philippe L Price D Song K James K 《The Journal of organic chemistry》2012,77(7):3099-3114
A general method for constraining peptide conformations via linkage of aromatic sidechains has been developed. Macrocyclization of suitably functionalized tri-, tetra- and pentapeptides via Suzuki-Miyaura cross-coupling has been used to generate side chain to side chain, biaryl-bridged 14- to 21-membered macrocyclic peptides. Biaryl bridges possessing three different configurations, meta-meta, meta-ortho, and ortho-meta, were systematically explored through regiochemical variation of the aryl halide and aryl boronate coupling partners, allowing fine-tuning of the resultant macrocycle conformation. Suzuki-Miyaura macrocyclizations were successfully achieved both in solution and on solid phase for all three sizes of peptide. This approach constitutes a means of constraining peptide conformation via direct carbogenic fusion of side chains of naturally occurring amino acids such as phenylalanine and tyrosine, and so is complementary to strategies involving non-natural, for example, hydrocarbon, bridges. 相似文献
956.
Herrmann C Salas PF Patrick BO de Kock C Smith PJ Adam MJ Orvig C 《Dalton transactions (Cambridge, England : 2003)》2012,41(21):6431-6442
This work presents a new family of organometallic antimalarial compounds consisting of ferrocene bearing a chloroquine-derived moiety as well as a 1,2;3,5-diisopropylidene glucofuranose moiety at a cyclopentadienyl scaffold in a 1,2-substitution pattern. The synthetic route proceeds via a stereoselective functionalization of ferrocene carboxaldehyde to the 1,2-disubstituted conjugates. After complete characterization of these new, trifunctional conjugates, they were examined for their cytotoxicity in two cancerous cell lines (MDA-MB-435S and Caco2) and one non-cancerous cell line (MCF-10A), showing that increased cytotoxicity can be observed for the chloroquine ferrocenyl conjugates compared to their carbohydrate-substituted precursors. The antiplasmodial activity of the conjugates in a chloroquine-sensitive strain of Plasmodium falciparum (D10) and a chloroquine-resistant strain (Dd2) was determined. Monosubstituted conjugates 13, 14 and 15 exhibit decreasing activity with increasing alkyl chain length between the ferrocene and quinoline moiety, bifunctional conjugates 16, 17, 18 show constant activity, performing better than chloroquine in the Dd2 strain. 相似文献
957.
Kamatchi TS Chitrapriya N Lee H Fronczek CF Fronczek FR Natarajan K 《Dalton transactions (Cambridge, England : 2003)》2012,41(7):2066-2077
With the aim to develop more efficient, less toxic, target specific metal drugs and evaluate their anticancer properties in terms of oxidation state and co-ligand sphere, a sequence of Ru(II), Ru(III) complexes bearing 4-hydroxy-pyridine-2,6-dicarboxylic acid and PPh(3)/AsPh(3) were synthesized and structurally characterized. Biological studies such as DNA binding, antioxidant assays and cytotoxic activity were carried out and their anticancer activities were evaluated. Interactions of the complexes with calf thymus DNA revealed that the triphenylphosphine complexes could bind more strongly than the triphenylarsine complexes. The free radical scavenging ability, assessed by a series of in vitro antioxidant assays involving DPPH radical, hydroxyl radical, nitric oxide radical, superoxide anion radical, hydrogen peroxide and metal chelating assay, showed that the Ru(III) complexes possess excellent radical scavenging properties compared to those of Ru(II). Cytotoxicity studies using three cancer lines viz HeLa, HepG2, HEp-2 and a normal cell line NIH 3T3 showed that Ru(II) complexes exhibited substantial cytotoxic specificity towards cancer cells. Furthermore, the Ru(II) complexes were found to be superior to Ru(III) complexes in inhibiting the growth of cancer cells. 相似文献
958.
959.
Professor Chris Linton 《Contemporary Physics》2013,54(2):157-158
When Oliver Cromwell's decision to place the Post Office under the control of Parliament was ratified by Charles II in 1660, the main business of the Post Office was communication—transmission of the written word by letter. Since these days the Post Office has become responsible for many other services, either on its own account, or as an agent for other Government Departments; communication, however, is still its main business, although many new forms of it have been added during the last hundred years. The first new form was that of the transmission of the written word in coded form by the electric telegraph; this was followed by transmission of the spoken word by telephone. Transmission of pictorial information came next: first in the slow-speed form of picture telegraphy, then in the high-speed form of television. The latest form is data transmission, the data being mostly numerical, which is associated with the growth of electronic computers over the last decade or so; the administrative and technical arrangements for data transmission by the Post Office are still in the very early stages, but this service will undoubtedly grow. 相似文献
960.