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21.
John M. Beierle W. Seth Horne Dr. Jan H. van Maarseveen Prof. Dr. Beatrice Waser Jean Claude Reubi Prof. Dr. M. Reza Ghadiri Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(26):4725-4729
A would‐be amide : A 1,4‐disubstituted 1,2,3‐triazole was used as a surrogate for a trans amide bond to create a library of 16 diastereomeric pseudotetrapeptides as β‐turn mimetics. High‐resolution structural analysis indicated that these scaffolds adopt distinct, rigid, conformationally homogeneous β‐turn‐like structures (see example), some of which bind somatostatin receptor subtypes selectively, and some of which show broad‐spectrum activity.
22.
Christos Economou Justin P. Romaire Tony Z. Scott Brendan T. Parr Seth B. Herzon 《Tetrahedron》2018,74(26):3188-3197
We recently reported a convergent strategy to access the polycyclic guanidinium alkaloid (+)-batzelladine B via an aldol addition–retro-aldol–aza-Michael addition cascade. Here we describe the application of this approach toward the total syntheses of (+)-batzelladine E, (?)-dehydrobatzelladine C, and (+)-batzelladine K. The identification of suitable methods to functionalize a common tropane core by electrophilic alkynylation and nucleophilic 1,2-addition were essential to generalizing this approach. We provide evidence for the intermediacy of an acylallene species in the cascade reaction. 相似文献
23.
Transient‐Ligand‐Enabled ortho‐Arylation of Five‐Membered Heterocycles: Facile Access to Mechanochromic Materials 下载免费PDF全文
Bijin Li Kapileswar Seth Ben Niu Lei Pan Huiwen Yang Prof. Dr. Haibo Ge 《Angewandte Chemie (International ed. in English)》2018,57(13):3401-3405
Reported herein is the first example of a direct arylation of heteroarenes by a transient‐ligand‐directed strategy without the need to construct and deconstruct the directing group. A wide range of heteroarenes undergoes the coupling with diverse aryl iodides to assemble a large library of highly selective and functionalized 3‐arylthiophene‐2‐carbaldehydes. This route provides an opportunity to rapidly access new mechanofluorochromic materials. Moreover, a novel strategy for mechanochromic luminogens with chromism trends of red‐ and blue‐shifts has been disclosed for the first time by facile functional‐group modifications to a common structural core. 相似文献
24.
John R. Van Camp Tish Young Rosemarie F. Hartman Seth D. Rose 《Photochemistry and photobiology》1987,45(3):365-370
Abstract— Photosensitized pyrimidine dimer splitting characterizes the enzymatic process of DNA repair by the DNA photolyases. Possible pathways for the enzymatic reaction include photoinduced electron transfer to or from the dimer. To study the mechanistic photochemistry of splitting by a sensitizer representative of excited state electron donors, a compound in which an indole is covalently linked to a pyrimidine dimer has been synthesized. This compound allowed the quantitative measurement of the quantum efficiency of dimer splitting to be made without uncertainties resulting from lack of extensive preassociation of the unlinked dimer and sensitizer free in solution. Irradiation of the compound with light at wavelengths absorbed only by the indolyl group (approximately 280 nm) resulted in splitting of the attached dimer. The quantum yield of splitting of the linked system dissolved in N2 0-saturated aqueous solution was found to be 0.04 ± 0.01. The fluorescence typical of indoles was almost totally quenched by the attached dimer. A splitting mechanism in which an electron is efficiently transferred intramolecularly from photoexcited indole to ground state dimer has been formulated. The surprisingly low quantum yield of splitting has been attributed to inefficient splitting of the resulting dimer radical anion. Insights gained from this study have important mechanistic implications for the analogous reaction effected by the DNA photolyases. 相似文献
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TRANSIENT INTERMEDIATES IN INTRAMOLECULARLY PHOTOSENSITIZED PYRIMIDINE DIMER SPLITTING BY INDOLE DERIVATIVES 总被引:1,自引:0,他引:1
Tish Young Sang-Tae Kim John R. Van Camp Rosemarie F. Hartman Seth D. Rose 《Photochemistry and photobiology》1988,48(5):635-641
Abstract— Intramolecularly photosensitized pyrimidine dimer splitting can serve as a model for some aspects of the monomerization of dimers in the enzyme-substrate complex composed of a photolyase and UV-damaged DNA. We studied compounds in which a pyrimidine dimer was covalently linked either to indole or to 5-methoxyindole. Laser flash photolysis studies revealed that the normally observed photoejection of electrons from the indole or the 5-methoxyindole to solvent was diminished by an order of magnitude for indoles with dimer attached (dimer-indole and dimer-methoxyindole). The fluorescence lifetime of dimer-indole in aqueous methanol was 0.85 ns, whereas that of the corresponding indole without attached dimer (tryptophol) was 9.7 ns. Similar results were obtained for the dimer-methoxyindole (0.53 ns) and 5-methoxytryptophol (4.6 ns). The quantum yield of dimer splitting for the dimer-methoxyindole (φ287 K7 = 0.08) was only slightly greater than the value found earlier for the dimer bearing the unsubstituted indole (4>2K7 = 0.04). Transient absorption spectroscopy also revealed lower yields of indole radical cations following laser flash photolysis of dimer-indole compared to the indole without attached dimer. Dimer-methoxyindole behaved similarly. These results are interpreted in terms of an enhanced rate of radiationless relaxation of the indole and methoxyindole excited singlet states in dimer-indoles. The possible quenching of the indole and methoxyindole excited states via electron abstraction by the covalently linked dimer is discussed. 相似文献
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The 3-alkylidene-3H-indole 1-oxide functional group found in the naturally occurring alkaloid avrainvillamide has been synthesized by a cross coupling-reductive condensation sequence and found to undergo reversible addition of oxygen- and sulfur-based nucleophiles. 相似文献
29.
Ko C Levine B Toniolo A Manohar L Olsen S Werner HJ Martínez TJ 《Journal of the American Chemical Society》2003,125(42):12710-12711
The photoisomerization mechanism of the neutral form of the photoactive yellow protein (PYP) chromophore is investigated using ab initio quantum chemistry and first-principles nonadiabatic molecular dynamics (ab initio multiple spawning or AIMS). We identify the nature of the two lowest-lying excited states, characterize the short-time behavior of molecules excited directly to S2, and explain the origin of the experimentally observed wavelength-dependent photoisomerization quantum yield. 相似文献
30.
The synthesis, structure, and spectroscopic characterization of a series of phenylacetylenylene rodlike molecules containing dipyrromethene (dipyrrin) ligands are described. The combination of the phenylacetylenylene groups with the porphyrinogenic dipyrrin moieties results in a rich absorption spectroscopy for these compounds, although the fluorescence of the phenylacetylenylene moiety is quenched by presence of the dipyrrin chelator. The Cu(2+) and Fe(3+) complexes of these ligands have been prepared and three of these compounds have been structurally characterized by using single-crystal X-ray diffraction. Unlike other octahedral metal-dipyrrin complexes described to date, one of the iron complexes demonstrates ideal threefold symmetry in the solid-state. The elongated structure and high symmetry of these complexes suggests the use of these meso-substituted phenylacetylenylene ligands as an interesting class of extended, branched molecules for the construction of supramolecular architectures. 相似文献