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101.
Alexander Chernega Dirk. L. Elend Christian A.P. Smethurst Paul M. Roberts Andrew D. Smith G. Darren Smyth 《Tetrahedron》2007,63(30):7036-7046
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
102.
Friedrich Bossert Horst Meyer Egbert Wehinger 《Angewandte Chemie (International ed. in English)》1981,20(9):762-769
The aryldihydropyridines first prepared by Hantzsch almost 100 years ago have recently been found to be highly effective calcium antagonists with suitable pharmacological profiles. An illustrative example is dimethyl-l,4-dihydro-2,6-dimethyl-4-(o-nitrophenyl)pyridine-3,5-dicarboxylate (Nifedipine) which is already employed therapeutically. This substance lowers the frequency of attack of angina pectoris and reduces blood pressure. The discovery of the therapeutic activity of this class of substances initiated renewed investigation of the Hantzsch condensation and the synthesis of numerous 4-aryldihydropyridines and related compounds. Qualitative and quantitative structure/activity relationships of these substances can be deduced from their biological data. 相似文献
103.
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
104.
Diekers M Luo C Guldi DM Hirsch A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(4):979-991
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
105.
SYNTHESIS OF POSITIVELY CHARGED PHTHALOCYANINES and THEIR ACTIVITY IN THE PHOTODYNAMIC THERAPY OF CANCER CELLS 总被引:1,自引:0,他引:1
D. Wöhrle N. Iskander G. Graschew H. Sinn E. A. Friedrich W. Maier-Borst J. Stern P. Schlag 《Photochemistry and photobiology》1990,51(3):351-356
Positively charged zinc containing or metal free phthalocyanines 6a-c and 7a-c were prepared via a three step procedure starting from 4-nitrophthalonitrile. The phthalocyanines contain alkyl chains of different length in order to influence the hydrophilic vs lipophilic character of the compounds. The partition between a hydrophilic (water) and lipophilic (octanol-1) phase was determined, and the photoredox activities were investigated. Initial results on the photodynamic activity of these compounds were compared with those of Dougherty's Photofrin II on different malignant and non-malignant cell lines (XP 29MAmal, CX1, HeLa, S180 and NO17). Positively charged phthalocyanines in vitro showed a higher photodynamic activity than Photofrin II. 相似文献
106.
Theoretical and experimental study of the adsorption on radioactive gases on continuous flow columns
A bimolecular reaction model was used to describe the adsorption process in continuous flow columns filled with solid adsorbents. The analytical solution of the model for low gas concentrations and a cascade-type numerical method for higher gas concentrations were developed. An air flow apparatus using activated carbon as adsorbent and methyl-iodide labelled with125I as adsorbate was constructed for measuring breakthrough- and accumulation curves. 相似文献
107.
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
108.
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
109.
Zusammenfassung Das Nicotellin enthält wahrscheinlich nicht, wie die meisten anderen Tabakalkaloide, 2 N-Atome in der Molekel, sondern hat die Formel C15H11N3. Es werden gewichtige Gründe dafür beigebracht, es als 3,2;6,3-Terpyridyl (I) aufzufassen. Diese Hypothese wird durch Synthese des damit isomeren 3,2;4,3-Terpyridyls (V) und Vergleich der Infrarotspektren der beiden Terpyridyle mit denen von 4 bekannten Bipyridylen gestützt. Betrachtungen über eine mögliche Synthese des Nicotellins in der Pflanze führen zu Versuchen, diese Synthese in vitro nachzuahmen; diese Versuche geben aber eine andere Verbindung, wahrscheinlich das 1,5-Di--pyridyl-pentadien-(1,4)-on-(3).Herrn Prof. Dr.L. Ebert zum 60. Geburtstage in aufrichtiger Verehrung gewidment. 相似文献
110.
Azomethine ylide 3 , generated by thermolysis of 3,4-diphenyl-Δ1-1,2,3-triazoline-5,5-dimethyldicarboxylate 1 , can be trapped by isonitriles to give 3-imino-1,4-diphenylazetidine-2,2-dimethyldicarboxylates 5 . The IR, 1H-NMR, 13C-NMR and mass spectral data of the new compounds are discussed. 相似文献