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51.
A practical route for the synthesis of new biologically active 5-HT(2 A) receptor antagonists has been developed. In only three catalytic steps, this class of central nervous system (CNS) active compounds can be synthesized efficiently with high diversity. As the initial step, an anti-Markovnikov addition of amines to styrenes provides an easy route to N-(arylalkyl)piperazines, which constitute the core structure of the active molecules. Here, base-catalyzed hydroamination reactions of styrenes with benzylated piperazine proceeded in high yield even at room temperature. After catalytic debenzylation, the free amines were successfully carbonylated with different aromatic and heteroaromatic halides and carbon monoxide to yield the desired compounds in good to excellent yields. The two key reactions, base-catalyzed hydroamination of styrenes and palladium-catalyzed aminocarbonylation of haloarenes/heterocycles, showed tolerance towards various functional groups, thereby demonstrating the potential to synthesize a wide variety of new derivatives of this promising class of pharmaceuticals.  相似文献   
52.
The crystal structures of the tetrahedral cluster compounds GaNb(4)S(8) and GaTa(4)Se(8) were determined by single-crystal X-ray diffraction. They crystallize in the cubic GaMo(4)S(8) structure type (F3m), which can be derived from the spinel type by shifting the metal atoms off the centers of the chalcogen octahedra along [111]. Electrical resistivity and magnetic susceptibility measurements show that the electronic conduction originates from hopping of localized unpaired electrons (S = (1)/(2)) among widely separated Nb(4) or Ta(4) clusters, and thus these materials represent a new class of Mott insulators. Under high pressure we find that GaNb(4)S(8) undergoes a transition from the Mott insulating to a superconducting state with T(C) up to 4 K at 23 GPa, similar to GaNb(4)Se(8) and GaTa(4)Se(8). High-pressure single-crystal X-ray studies of GaTa(4)Se(8) reveal that the superconducting transition is connected with a gradual decrease of the octahedral distortion with increasing pressure. DFT band structure calculations show that weakly coupled cluster orbitals are responsible for a high density of states at the Fermi level. The correct insulating magnetic ground state for GaNb(4)S(8) with mu(eff) = 1.73 mu(B) is for the first time achieved by the LDA+U method using U = 6 eV and rhombohedral symmetry.  相似文献   
53.
A three-step protocol for the asymmetric synthesis of a range of β-substituted Baylis-Hillman products has been developed. This procedure involves the diastereoselective conjugate addition of lithium (R)-N-methyl-N-(α-methylbenzyl)amide to an α,β-unsaturated ester to generate an N-protected β-amino ester in high de. Subsequent asymmetric aldol reaction via deprotonation with LDA, transmetallation with B(OMe)3 and addition of an aldehyde gives a range of syn-aldol products in moderate to high de. Purification of the syn-aldol products to homogeneity followed by tandem N-oxidation and Cope elimination gives the desired β-substituted Baylis-Hillman products in good yield and high de and ee.  相似文献   
54.
In this study we have compared different ligands containing three or more hetero-atoms (N, O and/or S) with respect to their ability to form tridentate complexes with a Tc-tricarbonyl moiety. Comparison of each ligand in a competition reaction with histidine first and then with each other compound allowed to rank the ligands according to their ability of complex formation with the [99mTc(CO)3]+ precursor from diethylenetriamine (most efficient of the studied ligands) to nitrilotriacetic acid (weakest complexing properties). The results provide insight in the structural requirements for the formation of stable Tc-tricarbonyl complexes and suggest preferred combinations and arrangements of the hetero-atoms involved in the complex formation. They also give a good indication which type of ligand is most appropriate to modify biomolecules for an efficient and stable labelling with a Tc-tricarbonyl moiety.  相似文献   
55.
For the first time several T(h)-symmetrical hexakisadducts of C(60) bearing up to six electro- and photoactive o-phenylene diamine or 9,10-dialkoxyanthracene moieties were synthesized and subjected to photoinduced electron/energy-transfer studies. Both donors form a densely packed pi-donor shell surrounding the fullerene core. In these novel core-shell ensembles (7 and 19), either an efficient energy transfer from the dialkoxyanthracene periphery, or an electron transfer from the o-phenylene diamine periphery transduces the flow of excited-state energy or electrons, respectively, to the fullerene moiety, which resides in the central core. Due to the relatively high reduction potential of the fullerene core, which is anodically shifted by approximately equal to 0.7 V, compared with that of pristine C(60), the outcome of these intramolecular reactions depends mainly on the donor ability of the peripheral system. Interestingly, the charge-separated state in the o-phenylene diamine heptad (7; tau=2380 ns in benzonitrile) is stabilized by a factor of 20 relative to the corresponding o-phenylene diamine dyad (6; tau=120 ns in benzonitrile), an effect that points unequivocally to the optimized storage of charges in this highly functionalized fullerene ensemble.  相似文献   
56.
Using ring closing metathesis (RCM) as the key operation, a rapid access to β-lactams fused to a sultam moiety of variable ring size was developed from low cost, commercially available starting materials. An efficient RCM of 4-vinyl-azetidin-2-ones to give 1-aza-bicyclo[4.2.0]oct-4-en-8-ones is also reported.  相似文献   
57.
Chiral N‐dienyl lactams are crucial building blocks for the synthesis of complex organic compounds. However, their generation is rather challenging. This paper reports the novel one‐pot reaction of (S)‐methyl pyroglutamate as the a mide component with different a ldehydes and d ienophiles (AAD reaction) to give novel chiral 1‐amido‐2‐cyclohexenes. The corresponding N‐dienyl lactams generated in situ undergo subsequent Diels–Alder reactions in good yield and diastereoselectivity. The scope and limitations of the three‐component protocol were investigated. X‐ray and NMR spectroscopic analysis of the products as well as DFT calculations of the intermediates were also performed to explain the observed stereoselectivity and structural features.  相似文献   
58.
Substituted 2-aminoindenes have been synthesized in almost quantitative yields by reactions of amines such as methylpiperazine, trimethylethylenediamine, 1,4-diaza-cycloheptane and N,N′-dimethylethylenediamine with 2-indanone. The 2-aminoindenes can be deprotonated and reacted with BrMn(CO)3(Py)2 to produce the respective aminoindenyl-cymantrenes in yields between 55–70%. The X-ray crystal structures of 2-(methylpiperazine)indenyl-cymantrene 5 (P1 , a = 12.667(3) Å, b = 16.630(3) Å, c = 17.382(3) Å, α = 72.70(3)°, β = 74.59(3)°, γ = 88.66(3)°, V = 3364.1(12) Å 3, Z = 8, R1(2σ(I)) = 4.02%, wR2(2σ(I)) = 10.30%) and the HClO4 adduct of 2-(trimethylethylenediamine)-indenyl-cymantrene 6 (Cc, a = 23.722(5) Å, b = 6.9080 Å, c = 13.264 Å, β = 111.77(3)°, V = 2018.6(7) Å 3, Z = 4, R1(2σ(I)) = 2.94%, wR2(2σ(I)) = 7.90%) were determined. In both complexes the indenyl-carbon bonded to nitrogen displays significantly longer bonds to manganese [223.5(3)–225.8(3) pm] than the other four carbon atoms [213.3(3)–219.1(3) pm]. The short indenyl-nitrogen bonds of 136.2(4) and 137.8(4) pm are indicative of a substantial multiple bond character. The complexation of Zn2+ by the nitrogen atoms of 6 results in significant shifts of the CO stretching frequencies.  相似文献   
59.
The various protonated forms of phenol (1), catechol (2), resorcinol (3), and hydroquinone (4) were explored by ab initio quantum chemical calculations at the MP2/6-31G(d) and B3LYP/6-31G(d) levels. Proton affinities (PA) of 1-4 were calculated by the combined G2(MP2,SVP) method, and their gas-phase basicities were estimated after calculation of the change in entropy on protonation. These theoretical data were compared with the corresponding experimental values determined in a high-pressure mass spectrometer. This comparison confirmed that phenols are essentially carbon bases and that protonation generally occurs in a position para to the hydroxyl group. Resorcinol is the most effective base (PA = 856 kJ mol-1) due to the participation of both oxygen atoms in the stabilization of the protonated form. Since protonation is accompanied by a freezing of the two internal rotations, a significant decrease in entropy is observed. The basicity of catechol (PA = 823 kJ mol-1) is due to the existence of an intramolecular hydrogen bond, which is strengthened upon protonation. The lower basicity of hydroquinone (PA = 808 kJ mol-1) is a consequence of the fact that protonation necessarily occurs in a position ortho to the hydroxyl group. When the previously published data are reconsidered and a corrected protonation entropy is used, a proton affinity value of 820 kJ mol-1 is obtained for phenol.  相似文献   
60.
Metal-chelating properties-in the ground and excited states-of fullerenocalix[4]arenes containing two malonamide substituents at the upper rim and four alkyl ester chains at the lower rim have been studied by means of steady-state absorption, fluorescence spectroscopy, and time-resolved transient absorption spectra. In particular, the influence that Ag+ enforces on the fullerene electronic spectra is due to direct interactions between Ag+ and the surface of C60. The effects stemming from Na+, Mg2+, and Ba2+, on the other hand, are indirect and are introduced through chelating the metal ions to the calix[4]arene moiety. They strongly depend on the molecular structure of the fullerenocalix[4]arenes. No spectroscopic evidence was obtained for any influence caused by Mn2+, although the malonamide groups provide good chelating ability even for this transition metal ion.  相似文献   
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