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21.
Imines of (1S,9S)-t-butyl-9-amino-octahydro-6,10-dioxo-6H-pyridazino[1,2-a][1,2]diazepine-1-carboxylate undergo thermal (toluene, 110°C) or LiBr-DBU catalysed (MeCN, room temperature) regio- and stereo-specific cycloaddition to a range of chiral dipolarophiles giving enantiopure spiro-cycloadducts in excellent yield. The reactions proceed via intermediate NH azomethine ylides and litho azomethine ylides, respectively and results in the multiplication of chiral centres from 2 (one of which is lost in the process) to 5. 相似文献
22.
The preparation of the η4-4-2,3,5,6-tetramethyl-1,4-benzoquinonecomplex [CO(C5Me5)(C10H12O2)] (I) is reported. Complex I undergoesreversible protonation to yield the 2-6-η-4-hydroxy-1-oxo-2,3,5,6-tetramethylcyclohexadienyl complex [Co(C5Me5)(C10H13O2)BF4 (II) and diprotonation to yield the η6-6-1,4-dihydroxy-2,3,5,6-tetramethylbenzene complex [Co(C5Me5)(C10H14O2)] (BF4)2 (III). Methylation of complex I with MeI/AgPF6 gives the 2---6-η-4-methoxy-1-oxo-2,3,5,6-tetramethylcyclohexadienyl complex [Co(C5Me5)(C11H15O2])PF6 (IV). In trifluoroacetic acid solution complex IV is protonated to form the η6-1-hydroxy-4-methoxy-2,3,5,6-tetramethylbenzene cation [Co(C5Me5)-(C11H16O2)]2+ 相似文献
23.
Factor Xa is a serine protease which activates thrombin and plays a key regulatory role in the blood-coagulation cascade. Factor Xa is at the crossroads of the extrinsic and intrinsic pathways of coagulation and, hence, has become an important target for the design of anti-thrombotics (inhibitors). It is not known to be involved in other processes than hemostasis and its binding site is different to that of other serine proteases, thus facilitating selective inhibition. The design of high-affinity selective inhibitors of factor Xa requires knowledge of the structural and dynamical characteristics of its active site. The three-dimensional structure of factor Xa was resolved by X-ray crystallography and refined at 2.2 Å resolution by Padmanabhan and collaborators. In this article we present results from molecular dynamics simulations of the catalytic domain of factor Xa in aqueous solution. The simulations were performed to characterise the mobility and flexibility of the residues delimiting the unoccupied binding site of the enzyme, and to determine hydrogen bonding propensities (with protein and with solvent atoms) of those residues in the active site that could interact with a substrate or a potential inhibitor. The simulation data is aimed at facilitating the design of high-affinity selective inhibitors of factor Xa. 相似文献
24.
The geometry of the linear molecule HBO, has been investigated within the restricted Hartree-Fock LCAO-MO-SCF approximation. The calculated bond lengths for the near Hartree-Fock calculation were R(H-B)=2.1913 bohr, R(B-O)=2.2284 bohr. Several one electron properties have been calculated for the minimum energy configuration. 相似文献
25.
[reaction: see text] The title alkaloid was synthesized in racemic form from 3,7-diallyl-2,4,6,8-tetraoxo-3,7-diazabicyclo[3.3.1]nonane (7) by a regioselective diallylation reaction followed by double ring-closing olefin metathesis and exhaustive reduction. Tetraoxobispidine 7 was itself prepared in three simple operations from dimethyl malonate. The entire sequence to alpha-isosparteine was conducted on a multigram scale and proceeded without recourse to chromatography. 相似文献
26.
Jones NA Nepogodiev SA MacDonald CJ Hughes DL Field RA 《The Journal of organic chemistry》2005,70(21):8556-8559
Described herein is the synthesis of 3-C-carboxy-5-deoxy-L-xylose (aceric acid), a rare branched-chain sugar found in the complex pectic polysaccharide rhamnogalacturonan-II. The key synthetic step in the construction of aceric acid was the stereoselective addition of 2-trimethylsilyl thiazole to 5-deoxy-1,2-O-isopropylidene-alpha-L-erythro-pentofuran-3-ulose (2), which was prepared from L-xylose. The thiazole group was efficiently converted into the required carboxyl group via conventional transformations. Aceric acid was also synthesized by dihydroxylation of a 3-C-methylene derivative of 2 followed by oxidation of the resulting hydroxylmethyl group. The C-2 epimer of aceric acid was also synthesized using thiazole addition chemistry, starting from L-arabinose. 相似文献
27.
Piasecki E Bresson S Lott B Bougault R Colin J Crema E Galin J Gatty B Genoux-Lubain A Guerreau D Horn D Jacquet D Jahnke U Jastrzebski J Kordyasz A Le Brun C Lecolley JF Louvel M Morjean M Paulot C Pienkowski L Pouthas J Quednau B Schröder WU Schwinn E Skulski W Töke J 《Physical review letters》1991,66(10):1291-1294
28.
Unstable transition metal compounds formed from hydridosilacyclobutanes are described: 1-methyl-1-silacyclobutane reacts with nonacarbonyldiiron to give the complexes [Fe(CO)4(H){H2}] and [(H)Me}(CO)4], and with bis(triphenylphosphine)(ethylene)platinum(0) to give [Pt(H)(PPh3)2{H2}]. 相似文献
29.
D. Colin Phillips Sandra Spewock William M. Alvino 《Journal of polymer science. Part A, Polymer chemistry》1976,14(5):1137-1150
4-Aminophthalic acid has been polymerized in almost quantitative yield to low molecular weight polymer by electrochemical initiation at a platinum anode. Systems involving the acid, amine salt, and the ammonium salt have been explored; the acid and/or the amine salt of the acid provides the best means of obtaining polymer. Maximum molecular weight is attained in a very short time at low current densities (~2 hr at 50 mA). Thermogravimetric data indicate a temperature stability comparable to polyamide-imide polymers (400°C). Long reaction times and high current densities decrease molecular weight and polymer yield. 相似文献
30.
Franken A Kilner CA Thornton-Pett M Kennedy JD 《Chemical communications (Cambridge, England)》2002,(18):2048-2049
Reaction of the [1-Ph-closo-1-CB9H(4)-6,7,8,9,10-I5]- anion with 4-MeC6H4MgBr in the presence of [PdCl2(PPh3)2] gives the [Pd2I2(P(C6H(4)-4-Me)3)4]2+ salt of the [1-Ph-closo-1-CB9H(4)-10-I-6,7,8,9-(C6H(4)-4-Me)4]- anion, which exhibits an unusual neutral supramolecular assembly in the solid state, in which the dipalladium dication is encapsulated by two four-armed 'tetrapus' anionic units; the anion also has potentialities for four-fold dendrimer construction. 相似文献