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61.
Kumar K Michalik D Garcia Castro I Tillack A Zapf A Arlt M Heinrich T Böttcher H Beller M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(3):746-757
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
62.
White-Morris RL Stender M Tinti DS Balch AL Rios D Attar S 《Inorganic chemistry》2003,42(10):3237-3244
The preparation and X-ray crystal structures of (CyNC)Au(I)CN, (n-BuNC)Au(I)CN, and (i-PrNC)Au(I)CN.0.5CH(2)Cl(2) are reported and compared with those of (MeNC)Au(I)CN and (t-BuNC)Au(I)CN, which were previously described. These linear molecules are all organized through aurophilic interactions into three structural classes: simple chains ((CyNC)Au(I)CN and (t-BuNC)Au(I)CN), side-by-side chains in which two strands make Au...Au contact with each other ((n-BuNC)Au(I)CN), and nets in which multiple aurophilic interactions produce layers of gold(I) centers ((i-PrNC)Au(I)CN and (MeNC)Au(I)CN). All of these five solids dissolve to produce colorless, nonluminescent solutions with similar UV/vis spectra. However, each of the solids displays a unique luminescence with emission maxima occurring in the range 371-430 nm. 相似文献
63.
Swart M Fonseca Guerra C Bickelhaupt FM 《Journal of the American Chemical Society》2004,126(51):16718-16719
Recently, Vakonakis and LiWang (J. Am. Chem. Soc. 2004, 126, 5688) reported experimental evidence for stronger hydrogen bonds in RNA A:U than in DNA A:T base pairs, which was based on differences in NMR shielding for adenine C2. We have analyzed the proposed correlation between NMR shielding and hydrogen-bond strength using density functional theory. Although we agree with the conclusion that A:U is more strongly bound, we find no correlation between the hydrogen-bond strength and the NMR shielding of C2. Our study shows that NMR merely probes the presence/absence of the methyl group in thymine/uracil, without any relation to the strength of the hydrogen bonds involved. In other words, one cannot infer the Watson-Crick hydrogen-bond strength from the NMR shielding constant of adenine C2. 相似文献
64.
65.
Reactions of 2- and 3-Phenyl Substituted Alkylalkylidene Iminium Ions in the Gas Phase The collision-induced fragmentations of 2- and 3-phenyl substituted alkylalkylidene iminium ions are reported. Besides the homolytic cleavage of the azaallyl bond a nucleophilic attack of the unsubstituted phenyl group at the iminium function is observed in the gas phase, yielding carbonium ions such as cyclopropanspirobenzenium ( 3 ), indanylium ( 10 ) and indenylium ions ( 11 ). 相似文献
66.
Williamson PT Verhoeven A Ernst M Meier BH 《Journal of the American Chemical Society》2003,125(9):2718-2722
Rotational-resonance magic-angle spinning NMR experiments are frequently used to measure dipolar couplings and to determine internuclear distances. So far most measurements were performed on samples containing isolated spin pairs. Thus, extensive structure elucidation, for example in biomolecules, requires the preparation of a whole set of doubly labeled samples. Here, we describe the analysis of the rotational-resonance polarization-exchange curves obtained from a single, uniformly labeled sample. It is shown experimentally that, at a magnetic field of 14.09 T, the rotational-resonance conditions in uniformly (13)C-labeled threonine are sufficiently narrow to permit the measurement of five distances between the four carbon spins with an accuracy of better than 10%. The polarization-exchange curves are analyzed using a modified two-spin model consisting of the two active spins. The modified model includes an additional offset in the final polarization, which comes from the coupling to the additional, passive, spins. The validity of this approach is experimentally verified for uniformly (13)C-labeled threonine. The broader applicability of such a model is demonstrated by numerical simulations which quantify the errors as a function of the most relevant parameters in the spin system. 相似文献
67.
Eshelby J Goessman M Parsons PJ Pennicott L Highton A 《Organic & biomolecular chemistry》2005,3(16):2994-2997
The construction of the fourteen membered ring present in galbonolide B 1 is reported. The 10,11-diene system present in the southern portion of has been constructed using an ester enolate rearrangement/silicon mediated fragmentation cascade, whilst the macrocycle has been synthesised following a Johnson rearrangement/mercury assisted ring closure protocol. 相似文献
68.
Sandra Hübner Dirk Michalik Dr. Haijun Jiao Dr. Helfried Neumann Dr. Stefan Klaus Dirk Strübing Dr. Anke Spannenberg Dr. Matthias Beller Prof. Dr. 《化学:亚洲杂志》2007,2(6):734-746
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
69.
Ernst M Detken A Böckmann A Meier BH 《Journal of the American Chemical Society》2003,125(51):15807-15810
Proteins are not always available in amounts desirable for solid-state magic-angle spinning (MAS) nuclear-magnetic resonance (NMR) spectroscopy. To maximize the signal-to-noise ratio achievable with small samples, the filling factor must be optimized by using small-diameter MAS rotors. These rotors have the added benefit of allowing higher radio frequency field amplitudes during polarization transfer steps and during decoupling periods as well as allowing higher spinning frequencies. We demonstrate the advantages of relatively fast MAS (30 kHz using a 2.5 mm rotor) compared to MAS at 12 kHz for the 10.4 kDa model protein Crh with 93 residues and show that the signal-to-noise ratio in two-dimensional correlation spectra can be significantly improved by taking advantage of optimized pulse sequences available with rapid MAS. 相似文献
70.
We apply the recently developed adaptive ensemble optimization technique to simulate dense Lennard-Jones fluids and a particle-solvent model by broad-histogram Monte Carlo techniques. Equilibration of the simulated fluid is improved by sampling an optimized histogram in radial coordinates that shifts statistical weight towards the entropic barriers between the shells of the liquid. Interstitial states in the vicinity of these barriers are identified with unprecedented accuracy by sharp signatures in the quickly converging histogram and measurements of the local diffusivity. The radial distribution function and potential of mean force are calculated to high precision. 相似文献