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Brisa Hurlocker Dr. Chunhua Hu Prof. K. A. Woerpel 《Angewandte Chemie (International ed. in English)》2015,54(14):4295-4298
The isolation and characterization of a trans‐oxasilacycloheptene is reported. Single‐crystal X‐ray crystallographic studies indicate a high level of strain and deviation from ideal geometry. Reactions with several electrophiles demonstrated the nucleophilicity of the C?C double bond, affording oxasilacycloheptane and tetrahydrofuran products as single diastereomers. 相似文献
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Hurlocker B Abascal NC Repka LM Santizo-Deleon E Smenton AL Baranov V Gupta R Bernard SE Chowdhury S Rojas CM 《The Journal of organic chemistry》2011,76(7):2240-2244
By using (N-tosyloxy)-3-O-carbamoyl-D-glucal 10, which removes the need for a hypervalent iodine(III) oxidant, we provide evidence for rhodium nitrenoid-mediated ipso C-H activation as the origin of a C3-oxidized dihydropyranone product 3. This system may be especially susceptible to such a pathway because of the ease of forming a cation upon hydride transfer to the rhodium-complexed acyl nitrene. 相似文献
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Dr. Prashanth K. Poddutoori Niloofar Zarrabi Dr. Andrey G. Moiseev Roger Gumbau‐Brisa Dr. Serguei Vassiliev Prof. Art van der Est 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(9):3148-3161
Two self‐assembled supramolecular donor–acceptor triads consisting of AlIII porphyrin (AlPor) with axially bound naphthalenediimide (NDI) as an acceptor and tetrathiafulvalene (TTF) as a secondary donor are reported. In the triads, the NDI and TTF units are attached to AlIII on opposite faces of the porphyrin, through covalent and coordination bonds, respectively. Fluorescence studies show that the lowest excited singlet state of the porphyrin is quenched through electron transfer to NDI and hole transfer to TTF. In dichloromethane hole transfer to TTF dominates, whereas in benzonitrile (BN) electron transfer to NDI is the main quenching pathway. In the nematic phase of the liquid crystalline solvent 4‐(n‐pentyl)‐4′‐cyanobiphenyl (5CB), a spin‐polarized transient EPR spectrum that is readily assigned to the weakly coupled radical pair TTF.+NDI.? is obtained. The initial polarization pattern indicates that the charge separation occurs through the singlet channel and that singlet–triplet mixing occurs in the primary radical pair. At later time the polarization pattern inverts as a result of depopulation of the states with singlet character by recombination to the ground state. The singlet lifetime of TTF.+NDI.? is estimated to be 200–300 ns, whereas the triplet lifetime in the approximately 350 mT magnetic field of the X‐band EPR spectrometer is about 10 μs. In contrast, in dichloromethane and BN the lifetime of the charge separation is <10 ns. 相似文献
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