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31.
Prochiral alkenes, aldehydes, and ketones constitute the most frequently used starting materials for enantioselective organic syntheses. Protocols often involve chiral binding agents or Lewis acids that can give two diastereomeric adducts, the ratios of which are measures of chiral recognition. With π adducts, the diastereomers differ in the enantioface of the C?C or O?C group bound to the Lewis acid. This review provides the first comprehensive analysis of such equilibria and related binding phenomena with chiral transition metal Lewis acids. An extensive body of data from the authors' laboratory for complexes of the pyramidal rhenium fragment [(η5?C5H5)Re(No)(PPh3)]+ ( I ) affords particular insight. Literature data for other complexes are also summarized. A general model for chiral recognition based upon the relative steric properties of four quadrants is presented. This enables binding selectivities to be individually and rationally optimized for different classes of ligands. Electronic effects are also identified and correlated with specific structural properties. Relationships between binding equilibria, reactivity, and product configurations are discussed. 相似文献
32.
Ning Luo J. Brian Hutchison Kristi S. Anseth Christopher N. Bowman 《Journal of polymer science. Part A, Polymer chemistry》2002,40(11):1885-1891
(Methacryloyl ethylenedioxycarbonyl) benzyl N,N‐diethyldithiocarbamate (HEMA‐E‐In) was synthesized and used as a monomer iniferter to develop a novel, photopatternable grafting technology. This molecule functions as both a methacrylic monomer and a photoiniferter (photoinitiator–transfer agent–terminator). The structure of HEMA‐E‐In was characterized by 1H NMR, Fourier transform infrared, and ultraviolet–visible spectroscopies. In the presence of the monomer iniferter, methyl methacrylate was polymerized by exposure to 365‐nm ultraviolet radiation, confirming the initiation capability of HEMA‐E‐In. After the copolymerization of HEMA‐E‐In into a methacrylate‐based polymer, attenuated total reflectance Fourier transform infrared spectra revealed that the photoiniferter functionality was present at the surface of this polymeric substrate. Photografting of poly(ethylene glycol) monomethacrylate monomer from the surface caused a significant change in the hydrophobicity of the surface as demonstrated by contact angle measurements. The novel monomer photoiniferter HEMA‐E‐In initiates the polymerization of bulk monomer and provides a reactive functionality that facilitates further initiation and polymer modification by the polymerization of different monomers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1885–1891, 2002 相似文献
33.
Abstract— A labile intermediate in the photolytic rearrangement of the antibacterial drug, metronidazole, was identified by isolating the product of photolysis of metronidazole benzoate in methanol. The intermediate, 1-hydroxyethyl-2-methyl-4-hydroxyimino-5-oxo-imidazole, was shown to act as a bidentate chelating agent for copper(II) ions, whereas metronidazole forms a weak monodentate complex. The intermediate may be relevant to the bioactivation mechanism of metronidazole. 相似文献
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36.
Brian F.G. Johnson Jack Lewis Martyn V. Twigg 《Journal of organometallic chemistry》1974,67(3):C75-C76
Photolysis of Ru3(CO)12 in the presence of donor ligands rapidly produces monomeric ruthenium species. 相似文献
37.
The reaction of the cluster complex HCC[Co2(CO)6]CCo3(CO)9 with (or without) BrCCo3(CO)9 under Cadiot-Chodkiewicz coupling conditions gave the unusual alkynyl carboxamide complex C2H5N(H)C(O)CC[Co2(CO)6]CCo3(CO)9 rather than a coupled product containing two tricobalt cluster units. Steric demands imposed by the Co3 cluster allow attack at the least hindered alkyne carbon and stabilise the formed ynamine, so allowing subsequent CO insertion. The product has been characterised by X-ray crystallography. 相似文献
38.
Ramnial T McKenzie I Gorodetsky B Tsang EM Clyburne JA 《Chemical communications (Cambridge, England)》2004,(9):1054-1055
One-electron oxidation of N-heterocyclic carbenes (NHCs) has been carried out using oxidising agents such as tetracyanoethylene (TCNE) and ferrocenium [Cp(2)Fe](+); the formation of carbene radical cations is postulated. 相似文献
39.
A flexible protein-peptide docking method has been designed to consider not only ligand flexibility but also the flexibility of the protein. The method is based on a Monte Carlo annealing process. Simulations with a distance root-mean-square (dRMS) virtual energy function revealed that the flexibility of protein side chains was as important as ligand flexibility for successful protein-peptide docking. On the basis of mean field theory, a transferable potential was designed to evaluate distance-dependent protein-ligand interactions and atomic solvation energies. The potential parameters were developed using a self-consistent process based on only 10 known complex structures. The effectiveness of each intermediate potential was judged on the basis of a Z score, approximating the gap between the energy of the native complex and the average energy of a decoy set. The Z score was determined using experimentally determined native structures and decoys generated by docking with the intermediate potentials. Using 6600 generated decoys and the Z score optimization criterion proposed in this work, the developed potential yielded an acceptable correlation of R(2) = 0.77, with binding free energies determined for known MHC I complexes (Class I Major Histocompatibility protein HLA-A(*)0201) which were not present in the training set. Test docking on 25 complexes further revealed a significant correlation between energy and dRMS, important for identifying native-like conformations. The near-native structures always belonged to one of the conformational classes with lower predicted binding energy. The lowest energy docked conformations are generally associated with near-native conformations, less than 3.0 Angstrom dRMS (and in many cases less than 1.0 Angstrom) from the experimentally determined structures. 相似文献
40.
The molecular geometry of perfluoro(methyloxirane) has been studied using gas-phase electron diffraction data, effective least-squares refinement of the structure being achieved with the aid of constraints to limit the number of variable parameters. With the CCF3 bond constrained to be 0.078 Å longer than the ring CC, the refined bond- length values CF (av.) = 1.323(2), CO (av.) = 1.410(8), and CC (ring) = 1.467(7) Å (g values, with e.s.d. in parentheses) were obtained; the angles between ring bonds and substituent CF bonds were CCF (av.) 121(1) and OCF (av.) 114(1)o, the corresponding parameters involving the bulkier CCF3 fragment being larger by 3o in each case [∠CCCF3 124(1)o∠OCCF3 117(2)o]. The remaining refined parameters were ∠CCF(of CF3) = 110.6(4)o and τ , a torsion angle defining the orientation of the CF bonds of the CF3 group with respect to ring bonds, = 29(2)o. Dependent bond angles possessed the values 62.7 (COC), 58.7 [OCC (ring)], 108.3 [FCF (CF3 group)], 114 [FCF (ring CF2)], and 111o (FCCF3). 相似文献