RESUMO
A UV light-induced photodimerization of 5-[(imidazol-1-yl)methyl]uracil using glutamate- and aspartate-derived cyclic dipeptides (2,5-diketopiperazines - DKPs) as templates was investigated. Dual salt bridge formation between imidazole side chains and carboxylic acids resulted in the preorganization of the uracil monomers and the preferential formation of the cis-syn photodimer.
RESUMO
[structure] A formal total synthesis of the natural product dysidiolide is described. Starting from a Diels-Alder reaction between an enoate and a Rawal diene, the cyclohexenone 4 was synthesized. A subsequent stereospecific methyl cuprate addition established the desired trans configuration in the cyclohexane 3. Wacker oxidation of the pentenyl side chain to the diketone 17 followed by an intramolecular aldol condensation led to the bicyclic enone 2, a key intermediate in a recently reported synthesis of dysidiolide.
Assuntos
4-Butirolactona/análogos & derivados , Inibidores Enzimáticos/síntese química , Fosfatases cdc25/antagonistas & inibidores , 4-Butirolactona/síntese química , Espectroscopia de Ressonância Magnética , Difração de Raios XRESUMO
The synthesis, X-ray structure, behavior in solution, and biological properties of the complex [SnMe2(PyTSC)(OAc)].HOAc (HPyTSC = pyridine-2-carbaldehydethiosemicarbazone) are reported. The tin atom of this complex is coordinated to an N,N,S-tridentate PyTSC- anion, to a monodentate acetate ion, and to the two methyl groups in an approximately pentagonal bipyramidal environment with a vacant equatorial position. The complex partially evolves in DMSO and in DMSO/CHxCl4-x (X = 1, 2) mixtures, giving HPyTSC and SnMe2(OAc)2. [SnMe2 (PyTSC)(OAc)].HOAc, [SnMe2(DAPTSC)], and [SnPh2(DAPTSC)].2DMF (H2DAPTSC = 2,6-diacetylpyridine bis(thiosemicarbazone)) all suppress proliferation of Friend erythroleukaemia cells (FLC). DMSO-induced differentiation of FLC is slightly suppressed by [SnMe2(DAPTSC)] and is unaffected by [SnPh2(DAPTSC)].2DMF and [SnMe2(PyTSC)(OAc)].HOAc.
Assuntos
Antineoplásicos/síntese química , Compostos Orgânicos de Estanho/síntese química , Animais , Antineoplásicos/química , Antineoplásicos/farmacologia , Diferenciação Celular/efeitos dos fármacos , Divisão Celular/efeitos dos fármacos , Cristalografia por Raios X , Vírus da Leucemia Murina de Friend , Leucemia Eritroblástica Aguda/tratamento farmacológico , Camundongos , Modelos Moleculares , Estrutura Molecular , Compostos Orgânicos de Estanho/química , Compostos Orgânicos de Estanho/farmacologia , Soluções , Espectrofotometria Infravermelho , Células Tumorais CultivadasRESUMO
The structural and spectroscopic properties of a new copper (II) complex of cinoxacin (HCx) have been investigated. The complex [Cu(Cx)2].2H2O crystallizes in the monoclinic system, space group P2(1)/c. The cell dimensions are: a = 7.998(2), b = 7.622(1), c = 18.955(6) A, beta = 94.38(2) degree, V = 1154.6(6) A3, Z = 2. The structure was refined to R = 0.051. The crystal is composed of [Cu(Cx)2] units and uncoordinated water molecules. The Cu(II) ion, at a center of symmetry, is coordinated to two cinoxacinate (Cx) ligands related by the inversion center. Each cinoxacinate acts as bidentate ligand bonded to the cation through its carboxylate oxygen atom and through its exocyclic carbonyl oxygen atom, resulting in a CuO4 chromophore in a crystallographically planar configuration. The complex was screened for its activity against several bacteria, showing the same antimicrobial activity as the corresponding ligand.
