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131.
Annegret Tillack Harald Trauthwein Christian G. Hartung Martin Eichberger Stephan Pitter Achim Jansen Matthias Beller 《Monatshefte für Chemie / Chemical Monthly》2000,131(12):1327-1334
Summary. The oxidative amination of styrene with secondary amines in the presence of cationic rhodium catalysts yields regiospecifically
the corresponding anti-Markovnikov enamines. Styrene as the hydrogen acceptor gave concomitantly ethylbenzene. In the presence of 1,5-cyclooctadiene (cod) preferential reduction to cyclooctene takes place. The addition of cod reduces the rate of the reaction, but also the amount of ethylbenzene produced. Here, for the first time the ratio of enamine:
ethylbenzene is > 1, which is favourable in case of more expensive styrene derivatives. A screening of various ligands for
oxidative amination reveals that hemilabile 2-(ω-phosphino-n-alkyl)-pyridines are superior ligands for this reaction compared to simple alkyl and aryl phosphines.
Received May 30, 2000. Accepted July 11, 2000 相似文献
132.
Achiral and chiral cationic palladium catalysts, modified with atropisomeric P?N ligands with different steric and electronic properties, can efficiently produce poly(styrene‐alt‐CO) with essentially complete regioregularity and variable tacticity, depending on the ligand geometry; the electronic effect on catalytic activity depends on the geometry of the ligand. 相似文献
133.
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135.
Dr. Thomas Lunkenbein Dr. Frank Girgsdies Anna Wernbacher Dr. Johannes Noack Dr. Gudrun Auffermann Akira Yasuhara Achim Klein‐Hoffmann Prof. Wataru Ueda Dr. Maik Eichelbaum Dr. Annette Trunschke Prof. Robert Schlögl Dr. Marc G. Willinger 《Angewandte Chemie (International ed. in English)》2015,54(23):6828-6831
Complex Mo,V‐based mixed oxides that crystallize in the orthorhombic M1‐type structure are promising candidates for the selective oxidation of small alkanes. The oxygen sublattice of such a complex oxide has been studied by annular bright field scanning transmission electron microscopy. The recorded micrographs directly display the local distortion in the metal oxygen octahedra. From the degree of distortion we are able to draw conclusions on the distribution of oxidation states in the cation columns at different sites. The results are supported by X‐ray diffraction and electron paramagnetic resonance measurements that provide integral details about the crystal structure and spin coupling, respectively. 相似文献
136.
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138.
Achim Blumensath 《Mathematical Logic Quarterly》2011,57(1):65-86
Aiming for applications in monadic second‐order model theory, we study first‐order theories without definable pairing functions. Our main results concern forking‐properties of sequences of indiscernibles. These turn out to be very well‐behaved for the theories under consideration (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
139.
Peptide nucleic acid (PNA) is a synthetic analogue of DNA, which has the same nucleobases as DNA but typically has a backbone based on aminoethyl glycine (Aeg). PNA forms duplexes by Watson Crick hybridization. The Aeg-based PNA duplexes adopt a chiral helical structure but do not have a preferred handedness because they do not contain a chiral center. An L-lysine situated at the C-end of one or both strands of a PNA duplex causes the duplex to preferably adopt a left-handed structure. We have introduced into the PNA duplexes both a C-terminal L-lysine and one or two PNA monomers that have a γ-(S)-methyl-aminoethyl glycine backbone, which is known to induce a preference for a right-handed structure. Indeed, we found that in these duplexes the γ-methyl monomer exerts the dominant chiral induction effect causing the duplexes to adopt a right-handed structure. The chiral PNA monomer had a 2,2':6',2'-terpyridine (Tpy) ligand instead of a nucleobase and PNA duplexes that contained one or two Tpys formed [Cu(Tpy)(2)](2+) complexes in the presence of Cu(2+). The CD spectroscopy studies showed that these metal-coordinated duplexes were right-handed due to the chiral induction effect exerted by the S-Tpy PNA monomer(s) except for the cases when the [Cu(Tpy)(2)](2+) complex was formed with Tpy ligands from two different PNA duplexes. In the latter case, the metal complex bridged the two PNA duplexes and the duplexes were left-handed. The results of this study show that the preferred handedness of a ligand-modified PNA can be switched as a consequence of metal coordination to the ligand. This finding could be used as a tool in the design of functional nucleic-acid based nanostructures. 相似文献
140.
Achim Steinbauer 《Journal of Complexity》1999,15(4):2175
We present a new method for the approximation of Wiener integrals and provide an explicit error bound for a class
of smooth integrands. The purely deterministic algorithm is a sequence of quadrature formulas for the Wiener measure, where the knots are piecewise linear functions. It uses ideas of Smolyak, as well as the multiscale decomposition of the Wiener measure due to Lévy and Ciesielski. For the class
we obtain n()max(1, 2−4), where n() is the number of integrand evaluations needed to guarantee an error at most for f
. 相似文献