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921.
A considerable improvement is reported in the iron-catalyzed ring-expansion reactions of epoxides generating tetrahydrofuran derivatives by formal insertion of an alkene. Optimization of the catalyst system revealed that a preformed [Fe(salen)] complex minimizes the formation of polymerization side-products so that increased yields of intermolecular reactions were obtained. However, more importantly, the scope of the reaction could also be enlarged considerably. The iron-catalyzed ring-expansion reaction can now be applied to some styrene oxide derivatives, acting as radical donors, as well as to a wide variety of acceptor-substituted acyclic alkenes and cyclic dienes that act as radical acceptors. The use of unsymmetrical radical acceptors led to interesting questions concerning the regiochemistry of the reactions. The conservation of the stereochemistry of the starting materials in the products was investigated through a study of the reactions of E- and Z-configured acceptor-substituted double bonds. The reactions of fumaric and maleic esters were performed and the ratios of diastereomeric and regioisomeric products were determined. 相似文献
922.
Steinmetz H Irschik H Kunze B Reichenbach H Höfle G Jansen R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(20):5822-5832
Two novel antibiotics, thuggacin A (1) and B (2), were isolated from the myxobacterium Sorangium cellulosum. 1 and 2 are unique thiazole-containing macrolides with side chains on both sides of the lactone group. Upon standing in solution, thuggacin A (1) rearranges by acyl migration of the lactone group to give a mixture with thuggacins B (2) and C (3). NOEs and vicinal coupling constants within the lactone ring provided distinct data for the generation of a structure model by PM3 calculations, which allowed an analysis of the conformation in solution and the relative configuration of six asymmetric centres. A minor sorangium metabolite was identified as 13-methyl-thuggacin A (4). Furthermore, two natural thuggacin variants, 5 and 6, were found in another myxobacterium, Chondromyces crocatus. In these variants, one side chain is replaced by a methyl group and a hydroxy group is repositioned to give a primary alcohol at the former methyl site, in an alpha position with respect to the thiazole ring. 1 proved to be active against clinical isolates and reference strains of Mycobacterium tuberculosis. Preliminary studies on the mechanism of action indicate inhibition of the cellular electron-transport chain. 相似文献
923.
Bringmann G Haagen Y Gulder TA Gulder T Heide L 《The Journal of organic chemistry》2007,72(11):4198-4204
Streptomyces cinnamonensis DSM 1042 produces the polyketide-isoprenoid compound furanonaphthoquinone I (FNQ I) and isoprenylated phenazines, predominantly endophenazine A. However, the recently identified biosynthetic gene cluster for these compounds only contains a single gene for a mevalonate pathway enzyme, that is, a putative mevalonate kinase gene. This is in strong contrast to all Streptomyces strains examined so far, where all six genes encoding the mevalonate pathway enzymes are clustered in a single operon of 6.8 kb and, thus, raised the question about the biosynthetic origin of the isoprenoid moieties of FNQ I and endophenazine A. In this study, we investigated the incorporation of [13C2]acetate and [2-13C]glycerol into FNQ I and endophenazine A. The results unequivocally prove that the isoprenoid building blocks of both compounds are predominantly formed via the mevalonate pathway (approximately 80%) but that the MEP pathway (approximately 20%) contributes to the biosynthesis of these molecules, too. In actinomycetes, this is the first experimentally proven example of the utilization of both biosynthetic routes for the formation of one single secondary metabolite. The incorporation pattern of [2-13C]glycerol was consistent with a "reverse" prenyl transfer, that is, with the formation of a C-C bond from C-3 of GPP to the polyketide nucleus of FNQ I. 相似文献
924.
Braun L Liptau P Kehr G Ugolotti J Fröhlich R Erker G 《Dalton transactions (Cambridge, England : 2003)》2007,(14):1409-1415
Treatment of acetonitrile (1 equiv.) with n-butyllithium (0.95 equiv.) followed by chlorodiphenylphosphine (0.95 equiv.) under optimised reaction conditions gave a ca. 60% yield of bis(diphenylphosphino)acetonitrile (dppmCN, 1). The bidentate ligand was employed in the synthesis of the four-membered chelate metal complexes (dppmCN)MCl(2) [M = Pd (6a), Pt (6b)] and (dppmCN)RuCp*(Cl) (7). A very active catalyst for bromobenzene/phenylboronic acid Suzuki-Miyaura coupling was in situ generated by treatment of Pd(OAc)(2) with bis(diphenylphosphino)acetonitrile [TOF (1 h) >600000]. 相似文献
925.
926.
927.
928.
Weber Alfred P. Seipenbusch Martin Thanner Christoph Kasper Gerhard 《Journal of nanoparticle research》1999,1(2):253-265
Nickel nanoparticles produced by spark discharges were used as aerosol catalyst for the formation of methane. The available surface area of the particles was determined using different methods. It was found that the surface area available for nitrogen adsorption and, therefore, for the methanation reaction remained virtually constant during restructuring of the agglomerates while the surface area based on the mobility was significantly reduced. In general, the reaction parameters such as activation energy and reaction rates agree well with the values for single nickel crystals and foils. At temperatures above 350°C the activation energy and the photoelectric activity of the particles decrease indicating the formation of graphite on the particle surface. Also the change of the work function points to the build up of multiple layers of graphite on the particle surface. The surprisingly low temperature for the surface deactivation may indicate an enhanced formation of carbon atoms at the surface. 相似文献
929.
Within the NRQCD factorization approach the production of heavy quarkonia can be calculated in perturbative QCD in terms
of a few production-process-independent NRQCD matrix elements. We test the universality of these long-distance matrix elements
by comparing their values as determined from charmonium production at , ep, and colliders, and in , , and B decays.
Received: 27 April 1998 / Published online: 22 March 1999 相似文献
930.
Gerhard Röhrle 《manuscripta mathematica》1999,98(1):9-20
For a linear algebraic group G over an algebraically closed field k and a parabolic subgroup P of G the modality of P is defined to be the maximal number of parameters upon which a family of G-orbits on Lie P
u
depends and it is denoted by mod P, where P
u
is the unipotent radical of P. The principal aim of this note is a generalization of two basic “monotonicity” results from [19] to positive characteristic:
(1) If Θ is a semisimple automorphism of G and P is Θ-stable, then mod P
\Θ≤ mod P. (2) If G is reductive, char k is a good prime for G, and H is a closed reductive subgroup of G normalized by a maximal torus T⊂P of G, then mod (P∩H)≤ mod P.
Received: 22 April 1998 / Revised version: 3 July 1998 相似文献