RESUMEN
A series of trifluoromethyl-substituted 3-alkoxypyridinol derivatives has been deprotected to furnish pyridine-3,4-diol derivatives in good yields. The X-ray crystal structure analysis proved that a 1:1 mixture of pyridine-3,4-diols and their pyridin-4-one tautomers exist in the solid state. Subsequent conversion into bis(perfluoroalkanesulfonate)s were smoothly achieved. The obtained compounds were used as substrates for palladium-catalyzed coupling reactions. Fluorescence measurements of the biscoupled products showed a maximum of emission in the violet region of the spectrum.
RESUMEN
The flexible three-component reaction of lithiated alkoxyallenes with nitriles and carboxylic acids provided a series of highly functionalised beta-alkoxy-beta-ketoenamide derivatives. Upon base induced cyclisation and conversion to 4-pyridyl nonaflates various palladium-catalysed coupling reactions could be employed. The efficacy of this approach to functionalised pyridine derivatives was demonstrated by a fairly short route to a key intermediate suitable for a Glenvastatin synthesis. After Sonogashira couplings of alkynes with 4-pyridyl nonaflates subsequent cyclisations led to highly fluorescent [2,3c]furopyridine derivatives, whereas Suzuki reactions afforded 4-pyridyl stilbenes and by photocyclisation a highly substituted benzoisoquinoline derivative.
RESUMEN
A series of γ-oxo esters suitably substituted with various styrene subunits was subjected to samarium diiodide-induced 8-endo-trig cyclizations. Efficacy, regioselectivity and stereoselectivity of these reactions via samarium ketyls strongly depend on the substitution pattern of the attacked alkene moiety. The stereoselectivity of the protonation of the intermediate samariumorganyl is also influenced by the structural features of the substrates. This systematic study reveals that steric and electronic factors exhibited by the alkene and ketone subunits are of high importance for the outcome of these cyclization reactions leading to highly substituted benzannulated cyclooctanol derivatives. In exceptional cases, 7-exo-trig cyclizations to cycloheptanol derivatives have been observed. In examples with high steric hindrance the ketyl-aryl coupling can be a competing process.
RESUMEN
The synthesis, crystal structure, and magnetic properties of two trinuclear oxo-centered carboxylate complexes are reported and discussed: [Cr3(mu3-O)(mu2-PhCOO)6(H2O)3]NO3.4H2O.2CH3OH (1) and [Cr3(mu3-O)(mu2-PhCOO)2(mu2-OCH2CH3)2(bpy)2(NCS)3] (2). For both complexes the crystal system is monoclinic, with space group C2/c for 1 and P1/n for 2. The structure of complex 1 consists of discrete trinuclear cations, associated NO3- anions, and lattice methanol and water molecules. The structure of complex 2 is built only by neutral discrete trinuclear entities. The most important feature of 2 is the unusual skeleton of the [Cr3O] core due to the lack of peripheral bridging ligands along one side of the triangular core, which is unique among the structurally characterized (mu3-oxo)trichromium(III) complexes. Magnetic measurements were performed in the 2-300 K temperature range. For complex 1, in the high-temperature region (T > 8 K), experimental data could be satisfactorily reproduced by using an isotropic exchange model, H = -2J12S1S2 - 2J13S1S3 - 2J23S2S3 (J12 = J13 = J23) with Jij = -10.1 cm(-1), g = 1.97, and TIP = 550 x 10(-6) emu mol(-1). The antisymmetric exchange interaction plays an important role in the magnetic behavior of the system, so in order to fit the experimental magnetic data at low temperature, a new magnetic model was used where this kind of interaction was also considered. The resulting fitting parameters are the following: Gzz = 0.25 cm(-1), delta = 2.5 cm(-1), and TIP = 550 x 10(-6) emu mol(-1). For complex 2, the experimental data could be satisfactorily reproduced by using an isotropic exchange model, H = -2J1(S1S2 + S1S3) - 2J2(S2S3) with J1 = -7.44 cm(-1), J2 = -51.98 cm(-1), and g = 1.99. The magnetization data allows us to deduce the ground term of S = 1/2, characteristic of equilateral triangular chromium(III) for complex 1 and S = 3/2 for complex 2, which is confirmed by EPR measurements.
RESUMEN
The complexes of general formula [ML]2[Mn(NCS)4](ClO4)2 (where M = Cu(II), Ni(II); L = N-dl-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene) were obtained and the crystal structures of both heteronuclear compounds were determined at 173 K. Complex [CuL]2[Mn(NCS)4](ClO4)2 (1) crystallizes in a monoclinic space group, C2/c, with a = 41.297(9) A, b = 7.571(2) A, c = 16.417(4) A, beta = 96.97(15) degrees, Z = 8, whereas complex [NiL]2[Mn(NCS)4](ClO4)2.H2O (2) crystallizes in a monoclinic space group, P2/c, with a = 21.018(5) A, b = 7.627(2) A, c = 16.295(4) A, beta = 104.47(1) degrees, Z = 4. The magnetic behaviour of (1) and (2) has been investigated over the temperature range 1.8-300 K. Complex (1) displays ferromagnetic coupling inside the trinuclear core of CuMnCu and compound (2) behaves like a mononuclear Mn(II) system. The magnetic properties of the second compound (2) with a similar trinuclear structure shows that Ni(II) ions have a diamagnetic character and a rather weak zero-field splitting at the central Mn(II) ion occurs. Finally, the magnitudes of the Cu(II)-M(II) interactions with M = Ni and Mn have been compared and qualitatively justified.
RESUMEN
In this report, we present the application of samarium diiodide induced cyclisations of naphthyl-substituted ketones towards an easy and stereoselective access to tri- and tetracyclic-functionalised compounds. Typical naphthalene derivatives were studied to investigate the scope and limitations of this novel cyclisation process. The model substrates studied demonstrate that the samarium ketyl cyclisations are essentially restricted to the formation of six-membered rings. The diastereoselectivity of these reactions is strongly influenced by the connection of the alkyl side chain to the naphthalene core. Gamma-naphth-1-yl-substituted ketones furnished cyclisation products, such as 17 or 22-26, as single diastereomers, whereas gamma-naphth-2-yl-substituted precursors gave mixtures of diastereomers--as demonstrated by the conversion of model compound 10 into tricyclic products 18 a/18 b, or that of cyclohexanone derivative 33 into tetracyclic diastereomers 34 a/34 b. Cyclic ketones as ketyl precursors furnished steroid-like tetracyclic skeletons; however, due to the cis/cis fusion of rings B/C and C/D these products have an "unnatural" bowl-like shape. Several of the cyclisation products have been identified by X-ray analyses, which not only proved the constitutions, but also the relative configurations and the preferred conformations. Steroid analogue 23 was subjected to subsequent transformations, which demonstrate that the styrene-like double bond of such compounds can be used for further structural diversification. First attempts to synthesise related azasteroids by incorporating nitrogen atoms into the ketone moiety are also reported. Thus, pyrrolidine derivatives 44 and 47 as well as piperidine derivatives 50 and 52 were subjected to samarium diiodide induced cyclisations. The expected tetracyclic products 48, 49 a/49 b, 51 and 53 a/53 b were obtained in moderate to good yields. The stereoselectivities observed follow the rules already established for the all-carbon precursors. The resulting products, bearing a nitrogen atom in ring D, are interesting azasteroid analogues with "unnatural" configuration.
Asunto(s)
Compuestos Aza/química , Yoduros/química , Cetonas/química , Compuestos Macrocíclicos/síntesis química , Naftalenos/química , Samario/química , Esteroides/química , Alquilación , Ciclización , Compuestos Macrocíclicos/química , Modelos Moleculares , Estructura Molecular , Nitrógeno/química , Pirrolidinas/química , EstereoisomerismoRESUMEN
Addition of lithiated methoxyallene to pivalonitrile afforded after aqueous workup the expected iminoallene 1 in excellent yield. Treatment of this intermediate with silver nitrate accomplished the desired cyclization to the electron-rich pyrrole derivative 2 in moderate yield. Surprisingly, trifluoroacetic acid converted iminoallene 1 to a mixture of enamide 3 and trifluoromethyl-substituted pyridinol 4 (together with its tautomer 5). A plausible mechanism proposed for this intriguing transformation involves addition of trifluoroacetate to the central allene carbon atom of an allenyl iminium intermediate as crucial step. Enamide 3 is converted to pyridinol 4 by an intramolecular aldol-type process. A practical direct synthesis of trifluoromethyl-substituted pyridinols 4, 10, 11, and 12 starting from typical nitriles and methoxyallene was established. Pyridinol 10 shows an interesting crystal packing with three molecules in the elementary cell and a remarkable helical supramolecular arrangement. Trifluoromethyl-substituted pyridinol 4 was converted to the corresponding pyridyl nonaflate 13, which is an excellent precursor for palladium-catalyzed reactions leading to pyridine derivatives 14-16 in good to excellent yields. The new synthesis of trifluoromethyl-substituted pyridines disclosed here demonstrates a novel reactivity pattern of lithiated methoxyallene which is incorporated into the products as the unusual tripolar synthon B.
RESUMEN
Based on our earlier results employing lithiated methoxyallene 2 as C(3) building block and imines 3 for the synthesis of dihydropyrrole derivatives 5, we have investigated chiral imines 6, 10, and 15 as electrophilic components. Combined with lithiated alkoxyallenes, these imines provide the corresponding primary adducts and finally the dihydropyrrole derivatives 8, 12, 17, 20, and 22 in good yields and with high to excellent syn selectivities. This stereochemical outcome is interpreted as a result of alpha-chelate control. Treatment with hydrochloric acid converted syn-8 and syn-12 into bicyclic compounds 9 and 13, whereas under more mildly acidic conditions adduct syn-17 was transformed into diol syn-18. The total synthesis of the uncommon gamma-amino acid (-)-detoxinine could be achieved by starting from (S)-malic acid, which was converted into imine 15 in four steps. Lithiated benzyloxyallene added to imine 15 and efficiently furnished the crucial dihydropyrrole derivative syn-22. The hydrogenolysis of this compound did not directly provide the protected triol 29 as anticipated, but a stepwise protocol made the triol available in a fairly satisfactory manner. A second crucial step of the synthesis was the selective oxidation of 29, which could be achieved by employing platinum dioxide and oxygen. The resulting bicyclic lactone 30 was smoothly transformed into enantiopure (-)-detoxinine. Thus, a fairly short synthesis of this natural product based on a lithiated alkoxyallene could be performed, demonstrating the potential of these intermediates for syntheses of interesting functionalized heterocyclic compounds.
Asunto(s)
Alcanos/química , Litio/química , Pirroles/química , Espectroscopía de Resonancia Magnética , Espectrometría de Masas , Modelos Moleculares , EstereoisomerismoRESUMEN
Polydentate bridging ligands can be used to link small polyoxo-alkoxo-metalate units to form supramolecular clusters. In the title compound, twelve µ4 -bridging squarato groups connect eight trinuclear methoxo-oxo-vanadate units to form a tetradodecanuclear cubic framework, in whose cavity six n-butyl groups of the tetra-n-butylammonium cations are anchored.
RESUMEN
We have studied the preparation and isolation of the halogenated alkylidene oxonium salts CH(3)OCHX(+)MF(6)(-) (X = Cl, F; M = As, Sb). Addition of dichloromethylmethylether at -78 degrees C to the superacidic media HF/MF(5) resulted in the formation of the chlorine compounds CH(3)OCHCl(+)MF(6)(-), whereas at -65 degrees C the fluorinated salts CH(3)OCHF(+)MF(6)(-) are formed by a chlorine/fluorine exchange. The salts are characterized by their low-temperature IR and Raman spectra. Additionally, the crystal structures of the hexafluoroantimonates are presented. The structures of the cations turned out to be different in some points. The salt CH(3)OCHF(+)SbF(6)(-) crystallizes in the monoclinic space group P2(1)/c with 4 molecules in the unit cell and a = 9.942(2), b = 7.454(2), and c = 10.297(3) Å; beta = 111.27(2) degrees. The salt CH(3)OCHCl(+)SbF(6)(-) crystallizes in the monoclinic space group P2(1)/c with 4 formula in the unit cell and a = 5.970(3), b = 12.019(5), and c = 10.994(5) Å; beta = 92.59(3) degrees.
RESUMEN
The largest isopolyoxotunstate ion known to date, W24 O8424- (structure shown in the picture), isolated as the cesium salt, and a chainlike polyoxotungstate ion made up of planar W4 O16 units, isolated as the sodium salt, hide behind the simple empirical formulas of the title compounds.