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31.
Carina I. Jette Irina Geibel Shoshana Bachman Masaki Hayashi Shunya Sakurai Hideki Shimizu Jeremy B. Morgan Brian M. Stoltz 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(13):4341-4345
Herein, we report the first Pd‐catalyzed enantioselective arylation of α‐substituted γ‐lactams. Two sets of conditions were developed for this transformation, allowing for the use of either aryl chlorides or bromides as electrophiles. Utilizing a highly electron‐rich dialkylphosphine ligand we have been able to construct α‐quaternary centers in good yields (up to 91 % yield) and high enantioselectivities (up to 97 % ee). 相似文献
32.
Olaya Domarco Claudia Kieler Christine Pirker Carina Dinhof Bernhard Englinger Johannes M. Reisecker Gerald Timelthaler Marcos D. García Carlos Peinador Bernhard K. Keppler Walter Berger Alessio Terenzi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(24):8091-8096
Metal‐driven self‐assembly afforded a multitude of fascinating supramolecular coordination complexes (SCCs) with applications as catalysts, host–guest, and stimuli‐responsive systems. However, the interest in the biological applications of SCCs is only starting to emerge and thorough characterization of their behavior in biological milieus is still lacking. Herein, we report on the synthesis and detailed in‐cell tracking of a Pt2L2 metallacycle. We show that our hexagonal supramolecule accumulates in cancer cell nuclei, exerting a distinctive blue fluorescence staining of chromatin resistant to UV photobleaching selectively in nucleolar G4‐rich regions. SCC co‐localizes with epitopes of the quadruplex‐specific antibody BG4 and replaces other well‐known G4 stabilizers. Moreover, the photophysical changes accompanying the metallacycle binding to G4s in solution (fluorescence quenching, absorption enhancement) also take place intracellularly, allowing its subcellular interaction tracking. 相似文献
33.
Dr. Lydia M. Peschel Carina Vidovič Dr. Ferdinand Belaj Dr. Dmytro Neshchadin Prof. Nadia C. Mösch-Zanetti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(15):3893-3902
The synthesis and structural determination of four tungsten alkyne complexes coordinated by the bio-inspired S,N-donor ligand 2-(4′,4′-dimethyloxazoline-2′-yl)thiophenolate (S-Phoz) is presented. A previously established protocol that involved the reaction of the respective alkyne with the bis-carbonyl precursor [W(CO)2(S-Phoz)2] was used for the complexes [W(CO)(C2R2)(S-Phoz)2] (R=H, 1 a ; Me, 1 b ; Ph, 1 c ). Oxidation with pyridine-N-oxide gave the corresponding W-oxo species [WO(C2R2)(S-Phoz)2] (R=H, 2 a ; Me, 2 b ; Ph, 2 c ). All W-oxo-alkyne complexes ( 2 a , b , c ) were found to be capable of alkyne release upon light irradiation to afford five-coordinate [WO(S-Phoz)2] ( 3 ). The photoinduced release of the alkyne ligand was studied in detail by in situ 1H NMR measurements, which revealed correlation of the photodissociation rate constant ( 2 b>2 a>2 c ) with the elongation of the alkyne C≡C bond in the molecular structures. Oxidation of [WO(S-Phoz)2] ( 3 ) with pyridine-N-oxide yielded [WO2(S-Phoz)2] ( 4 ), which shows highly fluxional behavior in solution. Variable-temperature 1H NMR spectroscopy revealed three isomeric forms with respect to the ligand arrangement versus each other. Furthermore, compound 4 rearranges to tetranuclear oxo compound [W4O4(μ-O)6(S-Phoz)4] ( 5 ) and dinuclear [{WO(μ-O)(S-Phoz)}2] ( 6 ) over time. The latter two were identified by single-crystal X-ray diffraction analyses. 相似文献
34.
The so-called ‘soldering’ procedure performed by Polyakov (Int J Math Phys A5, 833–842, 1990) for a -gauge theory is geometrically explained in terms of a Cartan connection on second-order frames of the projective space P1. The relationship between a Cartan connection and the usual (Ehresmann) connection on a principal bundle allows to gain an
appropriate insight into the derivation of the genuine ‘diffeomorphisms out of gauge transformations’ given by Polyakov himself.
Unité Mixte de Recherche (UMR 6207) du CNRS et des Universités Aix-Marseille I, Aix-Marseille II et de l’Université du Sud
Toulon-Var. Unité affiliée à la FRUMAM Fédération de Recherche 2291. 相似文献
35.
36.
Carina I. Jette Z. Jaron Tong Ryan G. Hadt Brian M. Stoltz 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(5):2049-2054
Herein, we report a Cu-catalyzed enantioselective allylic alkylation using a γ-butyrolactone-derived silyl ketene acetal. Critical to the development of this work was the identification of a novel mono-picolinamide ligand with the appropriate steric and electronic properties to afford the desired products in high yield (up to 96 %) and high ee (up to 95 %). Aryl, aliphatic, and unsubstituted allylic chlorides bearing a broad range of functionality are well-tolerated. Spectroscopic studies reveal that a CuI species is likely the active catalyst, and DFT calculations suggest ligand sterics play an important role in determining Cu coordination and thus catalyst geometry. 相似文献
37.
Absolute Configuration of Pharmaceutical Research Compounds Determined by X‐ray Powder Diffraction
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M. Sc. Carina Schlesinger M. Sc. Lukas Tapmeyer Dr. Silke D. Gumbert Dr. Dragica Prill Dr. Michael Bolte Prof. Dr. Martin U. Schmidt Dr. Christoph Saal 《Angewandte Chemie (International ed. in English)》2018,57(29):9150-9153
The absolute configuration of active pharmaceutical ingredients (APIs) was determined by generating salts of the active pharmaceutical ingredient (API) with counterions of known chirality, and determining the crystal structures by X‐ray powder diffraction. This approach avoids the (often tedious) growth of single crystals, and is successful with very limited quantities of material (less than 1 mg). The feasibility of the method is demonstrated on five examples, and its limitations are discussed as well. 相似文献
38.
Novel unsaturated ethers were synthesised in good yields starting from sucrose,using a two-step mild and efficient procedure based on the Gassman method, which consists in forming a vinyl group by the elimination of ethanol from mixed acetals with trimethylsilyl trifluoromethanesulfonate in the presence of alkyl amines. Mixed acetals are readily obtained from the corresponding alcohols and ethyl vinyl ether, using an acidic catalyst. Conventional etherification involving a primary halide was also examined. The monomers thus obtained were successfully polymerised by a free radical mechanism,yielding unbranched linear and soluble polymers with pending sucrose moieties, and some of their physical properties were determined. 相似文献
39.
Bäcktorp C Börje A Nilsson JL Karlberg AT Norrby PO Nyman G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(31):9549-9554
Pathways for formation of previously observed autoxidation products of ethoxylated surfactants have been studied by DFT (B3LYP). In addition to the established radical-chain reaction, several mechanistic possibilities for intramolecular fragmentation of the intermediate radicals have been characterized concerning reaction barriers and energies of transition states. The results can rationalize the formation of previously observed autoxidation products, including several, which have been implicated as strongly allergenic. 相似文献
40.
Keck GE Kraft MB Truong AP Li W Sanchez CC Kedei N Lewin NE Blumberg PM 《Journal of the American Chemical Society》2008,130(21):6660-6661
Highly potent bryostatin analogues which contain the complete bryostatin core structure have been synthesized using a pyran annulation approach as a key strategic element. The A ring pyran was assembled using a pyran annulation reaction between a C1-C8 hydroxy allylsilane and an aldehyde comprising C9-C13. This pyran was transformed to a new hydroxy allylsilane and then coupled with a preformed C ring aldehyde subunit in a second pyran annulation, with concomitant formation of the B ring. This tricyclic intermediate was elaborated to bryostatin analogues which displayed nanomolar to subnanomolar affinity for PKC, but displayed properties indistinguishable from a phorbol ester in a proliferation/attachment assay. 相似文献