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1.
Stefan Peterli Dieter Hubmann Urs Squin Helmut Mett Peter Traxler 《Helvetica chimica acta》1994,77(1):59-69
β-Nitrostyrene derivatives of adenosine 5′-glutarates are potent and selective bisubstrate-type inhibitors of the epidermal growth factor receptor protein tyrosine kinase (EGF-R PTK). In an attempt to improve the inhibitory activity, this type of compounds was modified with alkyl spacers of varying length between the nitrostyrene and the glutaryl units. The spacers consisted of 1, 3, 4, and 5 atoms to give compounds of the benzyl, oxyethyl, oxypropyl, and oxybutyl series, respectively (Schemes 1 and 2). Adenosine 5′-esters were prepared in the benzyl and oxypropyl series only. Compared to the compounds in the parent series without spacer (IC50 = 0.7–12 μM ), most of the modified compounds inhibited the EGF-R PTK only marginally or were inactive (IC50 ≥ 100 μM ). The only exceptions were the free acids 19 and 20 with IC50 values of ca. 5 μM . It is noteworthy that esterification of these two hydrogen glutarates with either MeOH or adenosine yielded inactive compounds, which is in contrast to the corresponding substances without spacers. 相似文献
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3.
Urs Lang 《Mathematische Zeitschrift》1992,210(1):581-592
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5.
Urs P. Wild Hans J. Griesser Vo Dinh Tuan Jean F.M. Oth 《Chemical physics letters》1976,41(3):450-455
The emission spectra of the second excited singlet state of [18] annulene and of monofluoro [18] annulene (in a 3-methylpentane glass at 4 K) are reported. The large energy gap between the first and second excited singlet states inhibits fast internal conversion and favours the appearance of S2 → S0 emission. In addition, fluorescence from the S1 state can be observed in monofluoro [13] annulene by exciting into the S2 or directly into the S1 absorption. 相似文献
6.
The photoelectron spectrum of tetrakis (methylidene)cyclobutane ( 1 , ‘[4]radialene’) is reported. The electronic states of 1 + are assigned on the basis of model calculations and with reference to related systems. Jahn-Teller activity in the degenerate states is discussed. A failure of the simple LCBO-model for the π(eg)-orbital of 1 is noted and traced to the fact that this orbital, though having a symmetry-equivalent π*-counterpart, does not interact with it. This feature is confined to [4n]radialenes; their total π-energies are therefore higher than those of the other members. It is shown that radialenes, in principle, do not constitute a class analogous to that of the linear polyenes as inferred earlier. 相似文献
7.
Dieter Seebach Stefan G. Müller Urs Gysel Jürg Zimmermann 《Helvetica chimica acta》1988,71(5):1303-1318
Preparative Chromatographic Resolution of Synthetically Useful Cyclic Acetals Racemic cyclic acetals derived from aldehydes and glycine, glycolic acid, thioglycolic acid, formylacetic acid, and acetoacetic acid (oxazolidinones 4 – 13 , dioxolanones 14 , 15 , oxathiolanone 16 , dioxinones 17 – 23 ) are resolved by preparative high-pressure liquid chromatography on silica gel coated with the polymer from N-acryloylphenylalanine ethyl ester (Chiraspher®). The separation factors α range from1,1 to 2,4. Use of a Prepbar®-chromatography system allows injection of several grams at a time. The enantiomeric acetals thus obtained are fully characterized. First application to amino-acid synthesis are mentioned. 相似文献
8.
On alkalinization of solutions of the chromiun(III)-aquo ion simple deprotonation takes place first. The degree of hydroxylation n OH however can be brought up to only about 1 (the exact value depending on the total concentration [Cr]t), before the uncharged complex Cr(OH)3(OH2)3 is precipitated. The structure of the very sparingly soluble complex (solubility ~10?7M ) is held together by hydrogen bonds of type I between the molecules, so that its formula may be written as Cr(OH)2H6/2-lattice. The formation of the well ordered structure is extremely fast. On aging, the metallic centers become connected by μ-hydroxo-bridges (type II) and the substances become amorphous and very insoluble. The dinuclear (H2O)4Cr(OH)2Cr(OH2)44+ behaves similar on deprotonation. Concerning the various equilibria constants see Table 1. 相似文献
9.
Two new enantioselective syntheses of the naphthopyranquinone antibiotic frenolicin B ( 1 ), of its enantiomer 2 , and of its diastereoisomers 3 and 4 were accomplished using two different routes from optically active β-Hydroxy esters (R)- and (S)- 11 and 18. β-Hydroxy esters (R)- and (S)- 11 were prepared stereoselectively from optically active sulfenylacetates (S)- and (R)- 10 , respectively (Scheme 2, Method A). Alternatively, compound 18 was obtained in excellent yield by enantioselective hydrogenation of the corresponding β-keto ester 17 , using a chiral ruthenium-complex catalyst (Scheme 3, Method B). Subsequently, compounds (S)- 11 and 18 were transformed into frenolicin B (1). In analogy, Stereoisomers 2–4 were prepared from (S)- and (R)- 11 in good yields. 相似文献
10.
Monodisperse Linear and Cyclic Oligo[(R)-3-hydroxybutanoates] Containing up to 128 Monomeric Units Using benzyl ester/(tert-butyl)diphenylsilyl ether protection, (COCl)2/pyridine esterification conditions, and a fragment-coupling strategy (with H2/Pd-C debenzylation and HF · pyridine desilylation), linear oligomers of (R)-3-hydroxybutanoic acid (3-HB) containing up to 128 3-HB building blocks (mol. weight > 11 000 Da) are assembled (Schemes 1,2,5, and 6). In contrast to the previously employed protecting-group combination, and due to the low-temperature esterifying conditions, this procedure leads to monodisperse oligomers: all steps occur without loss of single 3-HB units. The product oligomers with two, one, and no terminal protecting groups (mostly prepared in multi-gram amounts) are characterized by all standard spectroscopic methods, especially by mass spectroscopy (Figs. 2 and 3), by their optical activity, and by elemental analyses. Cyclization of the oligo[(R)-3-hydroxybutanoic acids] with up to 32 3-HB units, using thiopyridine activation and CuBr2 for the ring closure, produces oligolides consisting of up to 128 ring atoms (Scheme 7). Mixed oligolides containing 3-HB and (R)-3-hydroxypentanoic units are prepared from the corresponding linear trimers, using Yamaguchi's method for the ring closure (Scheme 8 and Fig.4 (X-ray crystal structures of two folded conformers)). Comparisons of melting points (Table 1), of [α] values (Tables 2 and 3), of 1H-NMR coupling constants (Table 3), and of molecular volume/hydroxyalkanoate unit (Table 4) of linear and cyclic oligomer derivatives and of the high-molecular-weigh polymer show that the monodisperse oligomers appear to be surprisingly good models for the polymer. Besides this insight, our synthesis is supplying the samples to further test the role of P(3-HB) (ca. 140 units) as a component of complexes forming channels through cell-wall phospholipid bilayers. 相似文献